Polymerizable absorbers of UV and high energy visible light

ABSTRACT

Described are polymerizable high energy light absorbing compounds of formula I: 
                         
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and X are as described herein. The compounds absorb various wavelengths of ultraviolet and/or high energy visible light and are suitable for incorporation in various products, such as biomedical devices and ophthalmic devices.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 62/736,496, filed Sep. 26, 2018, which is incorporated hereinby reference in its entirety.

FIELD OF THE INVENTION

The invention relates to UV and high energy visible light absorbers.More particularly, the invention relates to compounds with polymerizablefunctionality that absorb various wavelengths of UV and/or high energyvisible light, and yet are visibly transparent when incorporated in anarticle. Thus, the compounds may be used in polymeric articles,including biomedical devices, such as ophthalmic devices.

BACKGROUND OF THE INVENTION

High energy radiation from the sun, such as UV and high-energy visiblelight, is known to be responsible for cellular damage. While most of theradiation below 280 nm in wavelength is absorbed by the earth'satmosphere, photons possessing wavelengths ranging between 280 and 400nm have been associated with several ocular disorders including cornealdegenerative changes, and age-related cataract and macular degeneration.(See Statement on Ocular Ultraviolet Radiation Hazards in Sunlight,American Optometric Association, Nov. 10, 1993). The human corneaabsorbs some radiation up to 320 nm in wavelength (30% transmission)(Doutch, J. J., Quantock, A. J., Joyce, N. C., Meek, K. M, Biophys. J.,2012, 102, 1258-1264), but is inefficient in protecting the back of theeye from radiation ranging from 320 to 400 nm in wavelength.

Contact lens standards define the upper UV radiation wavelength at 380nm. The current Class I UV absorbing criteria defined by the AmericanOptometric Association require >99% of the radiation between 280 and 315nm (UV B) and >90% of the 316 to 380 nm (UV A) radiation to be absorbedby the contact lens. While the criteria effectively address absorptionof higher energy UV, there is little attention paid to the lower energyUV radiation (>380<400 nm) associated with retinal damage (Ham, W. T,Mueller, H. A., Sliney, D. H. Nature 1976; 260(5547):153-5) or to highenergy visible radiation.

High energy-visible light may also cause visual discomfort or circadianrhythm disruption. For example, computer and electronic device screens,flat screen televisions, energy efficient lights, and LED lights areknown to generate high energy visible light. Prolonged exposure to suchsources may cause eye strain. Viewing high energy visible light emittingdevices at night is also postulated to disrupt the natural circadianrhythm leading, for example, to inadequate sleep.

Absorption of high energy light before it reaches the eye continues tobe a desirable goal in the ophthalmics field. However, the extent towhich a particular wavelength range is absorbed is also important. Forinstance, in the UV A and UV B ranges, it may be desirable to absorb asmuch radiation as possible. On the other hand, since high energy visiblelight forms a part of the visible spectrum, complete absorption of suchlight may negatively affect vision. With high energy visible light,therefore, partial absorption may be more desirable.

There is a need for materials that provide targeted absorption ofundesirable wavelengths of high energy radiation, and that areprocessable into functional products. Compounds that absorb or attenuatehigh energy radiation, when used in ophthalmic devices, may help protectthe cornea, as well as the interior cells in the ocular environment,from degradation, strain, and/or circadian rhythm disruption.

SUMMARY OF THE INVENTION

The invention relates to high energy light absorbing compounds thatabsorb UV and/or high energy visible (HEV) light while substantiallytransmitting (e.g., greater than 80% transmission) at wavelengths longerthan about 450 nm. The compounds are therefore effective at providingtargeted absorption of high energy light, such as UV (UVA and UVB), lowenergy UV light (385 nm to 400 nm), and/or HEV (e.g., 400 to 450 nm).

The compounds are also polymerizable and are generally compatible withother raw materials, as well as the polymerization and processingconditions, that are used for making ophthalmic devices such as softcontact lenses. The compounds can therefore be readily covalentlyincorporated into the final product without the need for significantmodification of existing manufacturing processes and equipment.

Accordingly, in one aspect the invention provides a compound of formulaI:

wherein R¹, R² and R³ are independently H, C₁-C₆ alkyl, C₅-C₈cycloalkyl, C₁-C₆ alkoxy, aryl, aryloxy, halo, or —Y—P_(g); X is CR⁴R⁵,O, S, or NR⁴; R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently H, C₁-C₆alkyl, C₅-C₈ cycloalkyl, or —Y—P_(g); Y is a linking group; and P_(g) isa polymerizable group, wherein at least one of R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, and R⁹ is —Y—P_(g).

In another aspect, the invention provides an ophthalmic device that is afree radical reaction product of a reactive mixture comprising: one ormore monomers suitable for making the ophthalmic device; and apolymerizable high energy light absorbing compound comprising a compoundof formula I as described herein.

In a further aspect, the invention provides a method for making anophthalmic device.

The method comprises: (a) providing a reactive mixture containing acompound of formula I as described herein, one or more device formingmonomers, and a radical initiator; and (b) polymerizing the reactivemixture to form the ophthalmic device.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows UV-VIS Transmission Spectra of 0.2 mM methanol solutions ofexemplary Compounds (F) and (M).

FIGS. 2A and 2B show UV-VIS Transmission Spectra of Silicone HydrogelContact Lenses 4A-4E.

FIGS. 3A and 3B show UV-VIS Transmission Spectra of Silicone HydrogelContact Lenses 4A and 5A-C.

FIGS. 4A and 4B show UV-VIS Transmission Spectra of ConventionalHydrogel Lenses 6A-6E.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood that the invention is not limited to the detailsof construction or process steps set forth in the following description.The invention is capable of other embodiments and of being practiced orbeing carried out in various ways using the teaching herein.

As noted above, in one aspect, the invention provides UV/HEV absorbingcompounds. The compounds contain polymerizable functionality. It hasbeen discovered that ophthalmic devices that absorb substantial amountsof UV light as well as some amounts of HEV light can be readily preparedas described herein.

In addition, some known benzotriazole UV absorbing compounds, such asNORBLOC™, exhibit a window, in the range of about 250 to 280 nm, whereUV blocking is reduced. Advantageously, compounds of the inventioneliminate or significantly reduce this window.

Thus, compounds of the invention may successfully absorb UV (UVA, UVB),and/or HEV, while transmitting in the visible spectrum. The compoundsare polymerizable. The compounds therefore are suitable forincorporation in a variety of products, including biomedical devices andophthalmic devices.

With respect to the terms used in this disclosure, the followingdefinitions are provided.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention belongs. The polymer definitions areconsistent with those disclosed in the Compendium of Polymer Terminologyand Nomenclature, IUPAC Recommendations 2008, edited by: Richard G.Jones, Jaroslav Kahovec, Robert Stepto, Edward S. Wilks, Michael Hess,Tatsuki Kitayama, and W. Val Metanomski. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference.

As used herein, the term “(meth)” designates optional methylsubstitution. Thus, a term such as “(meth)acrylates” denotes bothmethacrylates and acrylates.

Wherever chemical structures are given, it should be appreciated thatalternatives disclosed for the substituents on the structure may becombined in any combination. Thus, if a structure contained substituentsR* and R**, each of which contained three lists of potential groups, 9combinations are disclosed. The same applies for combinations ofproperties.

When a subscript, such as “n” in the generic formula [***]_(n), is usedto depict the number of repeating units in a polymer's chemical formula,the formula should be interpreted to represent the number averagemolecular weight of the macromolecule.

The term “individual” includes humans and vertebrates.

The term “biomedical device” refers to any article that is designed tobe used while either in or on mammalian tissues or fluids, andpreferably in or on human tissue or fluids. Examples of these devicesinclude but are not limited to wound dressings, sealants, tissuefillers, drug delivery systems, coatings, adhesion prevention barriers,catheters, implants, stents, and ophthalmic devices such as intraocularlenses and contact lenses. The biomedical devices may be ophthalmicdevices, particularly contact lenses, most particularly contact lensesmade from silicone hydrogels or conventional hydrogels.

The term “ocular surface” includes the surface and glandular epitheliaof the cornea, conjunctiva, lacrimal gland, accessory lacrimal glands,nasolacrimal duct and meibomian gland, and their apical and basalmatrices, puncta and adjacent or related structures, including eyelidslinked as a functional system by both continuity of epithelia, byinnervation, and the endocrine and immune systems.

The term “ophthalmic device” refers to any device which resides in or onthe eye or any part of the eye, including the ocular surface. Thesedevices can provide optical correction, cosmetic enhancement, visionenhancement, therapeutic benefit (for example as bandages) or deliveryof active components such as pharmaceutical and nutraceuticalcomponents, or a combination of any of the foregoing. Examples ofophthalmic devices include but are not limited to lenses, optical andocular inserts, including but not limited to punctal plugs, and thelike. “Lenses” include soft contact lenses, hard contact lenses, hybridcontact lenses, intraocular lenses, and overlay lenses. The ophthalmicdevice may comprise a contact lens.

The term “contact lens” refers to an ophthalmic device that can beplaced on the cornea of an individual's eye. The contact lens mayprovide corrective, cosmetic, or therapeutic benefit, including woundhealing, the delivery of drugs or nutraceuticals, diagnostic evaluationor monitoring, ultraviolet light absorbing, visible light or glarereduction, or any combination thereof. A contact lens can be of anyappropriate material known in the art and can be a soft lens, a hardlens, or a hybrid lens containing at least two distinct portions withdifferent physical, mechanical, or optical properties, such as modulus,water content, light transmission, or combinations thereof.

The biomedical devices, ophthalmic devices, and lenses of the presentinvention may be comprised of silicone hydrogels or conventionalhydrogels. Silicone hydrogels typically contain at least one hydrophilicmonomer and at least one silicone-containing component that arecovalently bound to one another in the cured device.

“Target macromolecule” means the macromolecule being synthesized fromthe reactive monomer mixture comprising monomers, macromers,prepolymers, cross-linkers, initiators, additives, diluents, and thelike.

The term “polymerizable compound” means a compound containing one ormore polymerizable groups. The term encompasses, for instance, monomers,macromers, oligomers, prepolymers, cross-linkers, and the like.

“Polymerizable groups” are groups that can undergo chain growthpolymerization, such as free radical and/or cationic polymerization, forexample a carbon-carbon double bond which can polymerize when subjectedto radical polymerization initiation conditions. Non-limiting examplesof free radical polymerizable groups include (meth)acrylates, styrenes,vinyl ethers, (meth)acrylamides, N-vinyllactams, N-vinylamides,O-vinylcarbamates, O-vinylcarbonates, and other vinyl groups.Preferably, the free radical polymerizable groups comprise(meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinylamide, andstyryl functional groups, and mixtures of any of the foregoing. Morepreferably, the free radical polymerizable groups comprise(meth)acrylates, (meth)acrylamides, and mixtures thereof. Thepolymerizable group may be unsubstituted or substituted. For instance,the nitrogen atom in (meth)acrylamide may be bonded to a hydrogen, orthe hydrogen may be replaced with alkyl or cycloalkyl (which themselvesmay be further substituted).

Any type of free radical polymerization may be used including but notlimited to bulk, solution, suspension, and emulsion as well as any ofthe controlled radical polymerization methods such as stable freeradical polymerization, nitroxide-mediated living polymerization, atomtransfer radical polymerization, reversible addition fragmentation chaintransfer polymerization, organotellurium mediated living radicalpolymerization, and the like.

A “monomer” is a mono-functional molecule which can undergo chain growthpolymerization, and in particular, free radical polymerization, therebycreating a repeating unit in the chemical structure of the targetmacromolecule. Some monomers have di-functional impurities that can actas cross-linking agents. A “hydrophilic monomer” is also a monomer whichyields a clear single phase solution when mixed with deionized water at25° C. at a concentration of 5 weight percent. A “hydrophilic component”is a monomer, macromer, prepolymer, initiator, cross-linker, additive,or polymer which yields a clear single phase solution when mixed withdeionized water at 25° C. at a concentration of 5 weight percent. A“hydrophobic component” is a monomer, macromer, prepolymer, initiator,cross-linker, additive, or polymer which is slightly soluble orinsoluble in deionized water at 25° C.

A “macromolecule” is an organic compound having a number averagemolecular weight of greater than 1500, and may be reactive ornon-reactive.

A “macromonomer” or “macromer” is a macromolecule that has one groupthat can undergo chain growth polymerization, and in particular, freeradical polymerization, thereby creating a repeating unit in thechemical structure of the target macromolecule. Typically, the chemicalstructure of the macromer is different than the chemical structure ofthe target macromolecule, that is, the repeating unit of the macromer'spendent group is different than the repeating unit of the targetmacromolecule or its mainchain. The difference between a monomer and amacromer is merely one of chemical structure, molecular weight, andmolecular weight distribution of the pendent group. As a result, and asused herein, the patent literature occasionally defines monomers aspolymerizable compounds having relatively low molecular weights of about1,500 Daltons or less, which inherently includes some macromers. Inparticular, monomethacryloxypropyl terminated mono-n-butyl terminatedpolydimethylsiloxane (molecular weight=500-1500 g/mol) (mPDMS) andmono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminatedmono-n-butyl terminated polydimethylsiloxane (molecular weight=500-1500g/mol) (OH-mPDMS) may be referred to as monomers or macromers.Furthermore, the patent literature occasionally defines macromers ashaving one or more polymerizable groups, essentially broadening thecommon definition of macromer to include prepolymers. As a result and asused herein, di-functional and multi-functional macromers, prepolymers,and crosslinkers may be used interchangeably.

A “silicone-containing component” is a monomer, macromer, prepolymer,cross-linker, initiator, additive, or polymer in the reactive mixturewith at least one silicon-oxygen bond, typically in the form of siloxygroups, siloxane groups, carbosiloxane groups, and mixtures thereof.

Examples of silicone-containing components which are useful in thisinvention may be found in U.S. Pat. Nos. 3,808,178, 4,120,570,4,136,250, 4,153,641, 4,740,533, 5,034,461, 5,070,215, 5,244,981,5,314,960, 5,331,067, 5,371,147, 5,760,100, 5,849,811, 5,962,548,5,965,631, 5,998,498, 6,367,929, 6,822,016, 6,943,203, 6,951,894,7,052,131, 7,247,692, 7,396,890, 7,461,937, 7,468,398, 7,538,146,7,553,880, 7,572,841, 7,666,921, 7,691,916, 7,786,185, 7,825,170,7,915,323, 7,994,356, 8,022,158, 8,163,206, 8,273,802, 8,399,538,8,415,404, 8,420,711, 8,450,387, 8,487,058, 8,568,626, 8,937,110,8,937,111, 8,940,812, 8,980,972, 9,056,878, 9,125,808, 9,140,825,9,156,934, 9,170,349, 9,217,813, 9,244,196, 9,244,197, 9,260,544,9,297,928, 9,297,929, and European Patent No. 080539. These patents arehereby incorporated by reference in their entireties.

A “polymer” is a target macromolecule composed of the repeating units ofthe monomers used during polymerization.

A “homopolymer” is a polymer made from one monomer; a “copolymer” is apolymer made from two or more monomers; a “terpolymer” is a polymer madefrom three monomers. A “block copolymer” is composed of compositionallydifferent blocks or segments. Diblock copolymers have two blocks.Triblock copolymers have three blocks. “Comb or graft copolymers” aremade from at least one macromer.

A “repeating unit” is the smallest group of atoms in a polymer thatcorresponds to the polymerization of a specific monomer or macromer.

An “initiator” is a molecule that can decompose into radicals which cansubsequently react with a monomer to initiate a free radicalpolymerization reaction. A thermal initiator decomposes at a certainrate depending on the temperature; typical examples are azo compoundssuch as 1,1′-azobisisobutyronitrile and 4,4′-aobis(4-cyanovaleric acid),peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butylhydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroylperoxide, peracids such as peracetic acid and potassium persulfate aswell as various redox systems. A photo-initiator decomposes by aphotochemical process; typical examples are derivatives of benzil,benzoin, acetophenone, benzophenone, camphorquinone, and mixturesthereof as well as various monoacyl and bisacyl phosphine oxides andcombinations thereof.

A “cross-linking agent” is a di-functional or multi-functional monomeror macromer which can undergo free radical polymerization at two or morelocations on the molecule, thereby creating branch points and apolymeric network. Common examples are ethylene glycol dimethacrylate,tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,methylene bisacrylamide, triallyl cyanurate, and the like.

A “prepolymer” is a reaction product of monomers which containsremaining polymerizable groups capable of undergoing further reaction toform a polymer.

A “polymeric network” is a cross-linked macromolecule that can swell butcannot dissolve in solvents. “Hydrogels” are polymeric networks thatswell in water or aqueous solutions, typically absorbing at least 10weight percent water. “Silicone hydrogels” are hydrogels that are madefrom at least one silicone-containing component with at least onehydrophilic component. Hydrophilic components may also includenon-reactive polymers.

“Conventional hydrogels” refer to polymeric networks made fromcomponents without any siloxy, siloxane or carbosiloxane groups.Conventional hydrogels are prepared from reactive mixtures comprisinghydrophilic monomers. Examples include 2-hydroxyethyl methacrylate(“HEMA”), N-vinyl pyrrolidone (“NVP”), N, N-dimethylacrylamide (“DMA”)or vinyl acetate.

U.S. Pat. Nos. 4,436,887, 4,495,313, 4,889,664, 5,006,622, 5,039459,5,236,969, 5,270,418, 5,298,533, 5,824,719, 6,420,453, 6,423,761,6,767,979, 7,934,830, 8,138,290, and 8,389,597 disclose the formation ofconventional hydrogels. Commercially available conventional hydrogelsinclude, but are not limited to, etafilcon, genfilcon, hilafilcon,lenefilcon, nesofilcon, omafilcon, polymacon, and vifilcon, includingall of their variants.

“Silicone hydrogels” refer to polymeric networks made from at least onehydrophilic component and at least one silicone-containing component.Examples of silicone hydrogels include acquafilcon, asmofilcon,balafilcon, comfilcon, delefilcon, enfilcon, fanfilcon, formofilcon,galyfilcon, lotrafilcon, narafilcon, riofilcon, samfilcon, senofilcon,somofilcon, and stenfilcon, including all of their variants, as well assilicone hydrogels as prepared in U.S. Pat. Nos. 4,659,782, 4,659,783,5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,998,498, 6,087,415,5,760,100, 5,776,999, 5,789,461, 5,849,811, 5,965,631, 6,367,929,6,822,016, 6,867,245, 6,943,203, 7,247,692, 7,249,848, 7,553,880,7,666,921, 7,786,185, 7,956,131, 8,022,158, 8,273,802, 8,399,538,8,470,906, 8,450,387, 8,487,058, 8,507,577, 8,637,621, 8,703,891,8,937,110, 8,937,111, 8,940,812, 9,056,878, 9,057,821, 9,125,808,9,140,825, 9,156,934, 9,170,349, 9,244,196, 9,244,197, 9,260,544,9,297,928, 9,297,929 as well as WO 03/22321, WO 2008/061992, and US2010/0048847. These patents are hereby incorporated by reference intheir entireties.

An “interpenetrating polymeric network” comprises two or more networkswhich are at least partially interlaced on the molecular scale but notcovalently bonded to each other and which cannot be separated withoutbraking chemical bonds. A “semi-interpenetrating polymeric network”comprises one or more networks and one or more polymers characterized bysome mixing on the molecular level between at least one network and atleast one polymer. A mixture of different polymers is a “polymer blend.”A semi-interpenetrating network is technically a polymer blend, but insome cases, the polymers are so entangled that they cannot be readilyremoved.

The terms “reactive mixture” and “reactive monomer mixture” refer to themixture of components (both reactive and non-reactive) which are mixedtogether and, when subjected to polymerization conditions, form theconventional or silicone hydrogels of the present invention as well asbiomedical devices, ophthalmic devices, and contact lenses madetherefrom. The reactive monomer mixture may comprise reactive componentssuch as the monomers, macromers, prepolymers, cross-linkers, andinitiators, additives such as wetting agents, release agents, polymers,dyes, light absorbing compounds such as UV absorbers, pigments, dyes andphotochromic compounds, any of which may be reactive or non-reactive butare capable of being retained within the resulting biomedical device, aswell as pharmaceutical and nutraceutical compounds, and any diluents. Itwill be appreciated that a wide range of additives may be added basedupon the biomedical device which is made and its intended use.Concentrations of components of the reactive mixture are expressed asweight percentages of all components in the reactive mixture, excludingdiluent. When diluents are used, their concentrations are expressed asweight percentages based upon the amount of all components in thereactive mixture and the diluent.

“Reactive components” are the components in the reactive mixture whichbecome part of the chemical structure of the polymeric network of theresulting hydrogel by covalent bonding, hydrogen bonding, electrostaticinteractions, the formation of interpenetrating polymeric networks, orany other means.

The term “silicone hydrogel contact lens” refers to a hydrogel contactlens that is made from at least one silicone-containing compound.Silicone hydrogel contact lenses generally have increased oxygenpermeability compared to conventional hydrogels. Silicone hydrogelcontact lenses use both their water and polymer content to transmitoxygen to the eye.

The term “multi-functional” refers to a component having two or morepolymerizable groups. The term “mono-functional” refers to a componenthaving one polymerizable group.

The terms “halogen” or “halo” indicate fluorine, chlorine, bromine, andiodine.

“Alkyl” refers to an optionally substituted linear or branched alkylgroup containing the indicated number of carbon atoms. If no number isindicated, then alkyl (including any optional substituents on alkyl) maycontain 1 to 16 carbon atoms. Preferably, the alkyl group contains 1 to10 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 6carbon atoms, or alternatively 1 to 4 carbon atoms. Examples of alkylinclude methyl, ethyl, propyl, isopropyl, butyl, iso-, sec- andtert-butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, and the like. Examplesof substituents on alkyl include 1, 2, or 3 groups independentlyselected from hydroxy, amino, amido, oxa, carboxy, alkyl carboxy,carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halogen, phenyl,benzyl, and combinations thereof. “Alkylene” means a divalent alkylgroup, such as —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂CH(CH₃)CH₂—, and—CH₂CH₂CH₂CH₂—.

“Haloalkyl” refers to an alkyl group as defined above substituted withone or more halogen atoms, where each halogen is independently F, C₁, Bror I. A preferred halogen is F. Preferred haloalkyl groups contain 1-6carbons, more preferably 1-4 carbons, and still more preferably 1-2carbons. “Haloalkyl” includes perhaloalkyl groups, such as —CF₃— or—CF₂CF₃—. “Haloalkylene” means a divalent haloalkyl group, such as—CH₂CF₂—.

“Cycloalkyl” refers to an optionally substituted cyclic hydrocarboncontaining the indicated number of ring carbon atoms. If no number isindicated, then cycloalkyl may contain 3 to 12 ring carbon atoms.Preferred are C₃-C₈ cycloalkyl groups, C₃-C₈ cycloalkyl, more preferablyC₄-C₈ cycloalkyl, and still more preferably C₅-C₆ cycloalkyl. Examplesof cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl. Examples of substituents on cycloalkylinclude 1, 2, or 3 groups independently selected from alkyl, hydroxy,amino, amido, oxa, carbonyl, alkoxy, thioalkyl, amido, carbamate,carbonate, halo, phenyl, benzyl, and combinations thereof.“Cycloalkylene” means a divalent cycloalkyl group, such as1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene.

“Heterocycloalkyl” refers to a cycloalkyl ring or ring system as definedabove in which at least one ring carbon has been replaced with aheteroatom selected from nitrogen, oxygen, and sulfur. Theheterocycloalkyl ring is optionally fused to or otherwise attached toother heterocycloalkyl rings and/or non-aromatic hydrocarbon ringsand/or phenyl rings. Preferred heterocycloalkyl groups have from 5 to 7members. More preferred heterocycloalkyl groups have 5 or 6 members.Heterocycloalkylene means a divalent heterocycloalkyl group.

“Aryl” refers to an optionally substituted aromatic hydrocarbon ringsystem containing at least one aromatic ring. The aryl group containsthe indicated number of ring carbon atoms. If no number is indicated,then aryl may contain 6 to 14 ring carbon atoms. The aromatic ring mayoptionally be fused or otherwise attached to other aromatic hydrocarbonrings or non-aromatic hydrocarbon rings. Examples of aryl groups includephenyl, naphthyl, and biphenyl. Preferred examples of aryl groupsinclude phenyl. Examples of substituents on aryl include 1, 2, or 3groups independently selected from alkyl, hydroxy, amino, amido, oxa,carboxy, alkyl carboxy, carbonyl, alkoxy, thioalkyl, carbamate,carbonate, halo, phenyl, benzyl, and combinations thereof. “Arylene”means a divalent aryl group, for example 1,2-phenylene, 1,3-phenylene,or 1,4-phenylene.

“Heteroaryl” refers to an aryl ring or ring system, as defined above, inwhich at least one ring carbon atom has been replaced with a heteroatomselected from nitrogen, oxygen, and sulfur. The heteroaryl ring may befused or otherwise attached to one or more heteroaryl rings, aromatic ornonaromatic hydrocarbon rings or heterocycloalkyl rings. Examples ofheteroaryl groups include pyridyl, furyl, and thienyl. “Heteroarylene”means a divalent heteroaryl group.

“Alkoxy” refers to an alkyl group attached to the parent molecularmoiety through an oxygen bridge. Examples of alkoxy groups include, forinstance, methoxy, ethoxy, propoxy and isopropoxy. “Thioalkyl” means analkyl group attached to the parent molecule through a sulfur bridge.Examples of thioalkyl groups include, for instance, methylthio,ethylthio, n-propylthio and iso-propylthio. “Aryloxy” refers to an arylgroup attached to a parent molecular moiety through an oxygen bridge.Examples include phenoxy. “Cyclic alkoxy” means a cycloalkyl groupattached to the parent moiety through an oxygen bridge.

“Alkylamine” refers to an alkyl group attached to the parent molecularmoiety through an —NH bridge. Alkyleneamine means a divalent alkylaminegroup, such as —CH₂CH₂NH—.

“Siloxanyl” refers to a structure having at least one Si—O—Si bond.Thus, for example, siloxanyl group means a group having at least oneSi—O—Si group (i.e. a siloxane group), and siloxanyl compound means acompound having at least one Si—O—Si group. “Siloxanyl” encompassesmonomeric (e.g., Si—O—Si) as well as oligomeric/polymeric structures(e.g., —[Si—O]_(n)—, where n is 2 or more). Each silicon atom in thesiloxanyl group is substituted with independently selected R^(A) groups(where R^(A) is as defined in formula A options (b)-(i)) to completetheir valence.

“Silyl” refers to a structure of formula R³Si— and “siloxy” refers to astructure of formula R³Si—O—, where each R in silyl or siloxy isindependently selected from trimethylsiloxy, C₁-C₈ alkyl (preferablyC₁-C₃ alkyl, more preferably ethyl or methyl), and C₃-C₈ cycloalkyl.

“Alkyleneoxy” refers to groups of the general formula -(alkylene-O)_(p)—or —(O-alkylene)_(p)-, wherein alkylene is as defined above, and p isfrom 1 to 200, or from 1 to 100, or from 1 to 50, or from 1 to 25, orfrom 1 to 20, or from 1 to 10, wherein each alkylene is independentlyoptionally substituted with one or more groups independently selectedfrom hydroxyl, halo (e.g., fluoro), amino, amido, ether, carbonyl,carboxyl, and combinations thereof. If p is greater than 1, then eachalkylene may be the same or different and the alkyleneoxy may be inblock or random configuration. When alkyleneoxy forms a terminal groupin a molecule, the terminal end of the alkyleneoxy may, for instance, bea hydroxy or alkoxy (e.g., HO—[CH₂CH₂O]_(p)— or CH₃O—[CH₂CH₂O]_(p)—).Examples of alkyleneoxy include polyethyleneoxy, polypropyleneoxy,polybutyleneoxy, and poly(ethyleneoxy-co-propyleneoxy).

“Oxaalkylene” refers to an alkylene group as defined above where one ormore non-adjacent CH₂ groups have been substituted with an oxygen atom,such as —CH₂CH₂OCH(CH₃)CH₂—. “Thiaalkylene” refers to an alkylene groupas defined above where one or more non-adjacent CH₂ groups have beensubstituted with a sulfur atom, such as —CH₂CH₂SCH(CH₃)CH₂—.

The term “linking group” refers to a moiety that links a polymerizablegroup to the parent molecule. The linking group may be any moiety thatis compatible with the compound of which it is a part, and that does notundesirably interfere with the polymerization of the compound, is stableunder the polymerization conditions as well as the conditions for theprocessing and storage of the final product. For instance, the linkinggroup may be a bond, or it may comprise one or more alkylene,haloalkylene, amide, amine, alkyleneamine, carbamate, ester (—CO₂—),arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy,oxaalkylene, thiaalkylene, haloalkyleneoxy (alkyleneoxy substituted withone or more halo groups, e.g., —OCF₂—, —OCF₂CF₂—, —OCF₂CH₂—), siloxanyl,alkylenesiloxanyl, or combinations thereof. The linking group mayoptionally be substituted with 1 or more substituent groups. Suitablesubstituent groups may include those independently selected from alkyl,halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, MeO-alkyleneoxy,siloxanyl, siloxy, siloxy-alkyleneoxy-,siloxy-alkylene-alkyleneoxy-(where more than one alkyleneoxy groups maybe present and wherein each methylene in alkylene and alkyleneoxy isindependently optionally substituted with hydroxyl), ether, amine,carbonyl, carbamate, and combinations thereof. The linking group mayalso be substituted with a further polymerizable group, such as(meth)acrylate (in addition to the polymerizable group to which thelinking group is linked).

Preferred linking groups include C₁-C₈ alkylene (preferably C₂-C₆alkylene) and C₁-C₈ oxaalkylene (preferably C₂-C₆ oxaalkylene), each ofwhich is optionally substituted with 1 or 2 groups independentlyselected from hydroxyl and siloxy. Preferred linking groups also includecarboxylate, amide, C₁-C₈ alkylene-carboxylate-C₁-C₈ alkylene, or C₁-C₈alkylene-amide-C₁-C₈ alkylene.

When the linking group is comprised of combinations of moieties asdescribed above (e.g., alkylene and cycloalkylene), the moieties may bepresent in any order. For instance, if in Formula E below, L isindicated as being -alkylene-cycloalkylene-, then Rg-L may be eitherRg-alkylene-cycloalkylene-, or Rg-cycloalkylene-alkylene-.Notwithstanding this, the listing order represents the preferred orderin which the moieties appear in the compound starting from the terminalpolymerizable group (e.g., Rg or Pg) to which the linking group isattached. For example, if in Formula E, L and L² are indicated as bothbeing alkylene-cycloalkylene, then Rg-L is preferablyRg-alkylene-cycloalkylene- and -L²-Rg is preferably-cycloalkylene-alkylene-Rg.

The terms “high energy radiation absorber,” “UV/HEV absorber,” or “highenergy light absorbing compound” refer to chemical materials that absorbvarious wavelengths of ultraviolet light, high energy visible light, orboth. A material's ability to absorb certain wavelengths of light can bedetermined by measuring its UV/Vis transmission spectrum. Compounds thatexhibit no absorption at a particular wavelength will exhibitsubstantially 100 percent transmission at that wavelength. Conversely,compounds that completely absorb at a particular wavelength will exhibitsubstantially 0% transmission at that wavelength. If the amount of amaterial's transmission is indicated as a percentage for a particularwavelength range, it is to be understood that the material exhibits thepercent transmission at all wavelengths within that range.

Unless otherwise indicated, ratios, percentages, parts, and the like areby weight.

Unless otherwise indicated, numeric ranges, for instance as in “from 2to 10,” are inclusive of the numbers defining the range (e.g., 2 and10).

As noted above, in one aspect the invention provides UV/HEV absorbingcompounds of formula I:

wherein R¹, R² and R³ are independently H, C₁-C₆ alkyl, C₅-C₈cycloalkyl, C₁-C₆ alkoxy, aryl, aryloxy, halo, or —Y—P_(g);

X is CR⁴R⁵, O, S, or NR⁴;

R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently H, C₁-C₆ alkyl, C₅-C₈cycloalkyl, or —Y—P_(g);

Y is a linking group; and

P_(g) is a polymerizable group,

wherein at least one of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ is—Y—P_(g).

Formula I-1. Compounds of formula I may include compounds of formulaI-1, which are compounds of formula I wherein the compound contains oneor two independent —Y—P_(g) groups. Preferably, the compound containsone —Y—P_(g) group.

I-2. Preferred compounds of formulae I and I-1 include compounds offormula I-1, which are compounds of formula I or I-1 wherein R¹ is—Y—P_(g).

I-3. Preferred compounds of formulae I, I-1, and I-2 include compoundsof formula I-3, which are compounds of formula I, I-1, or I-2 wherein R²and R³ are independently H or C₁-C₆ alkyl. Preferably, R² and R³ areeach H.

I-4. Preferred compounds of formulae I, I-1, I-2, and I-3 includecompounds of formula I-4, which are compounds of formula I, I-1, 1-2, orI-3 wherein R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently H or C₁-C₆alkyl. Preferably, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are each H.

I-5. Preferred compounds of formulae I, I-1, I-2, I-3, and I-4 includecompounds of formula I-5, which are compounds of formula I, I-1, I-2,I-3, or I-4 wherein X is CH₂, O, NH, or NCH₃. Preferred compoundsinclude those where X is CH₂. Preferred compounds also include thosewhere X is O.

I-6. Preferred compounds of formulae I, I-1, I-2, I-3, I-4, and I-5include compounds of formula I-6, which are compounds of formula I, I-1,I-2, I-3, I-4, or I-5 wherein P_(g) (a polymerizable group) is styryl,vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam,N-vinylamide, (meth)acrylate, or (meth)acrylamide. Preferably, P_(g) is(meth)acrylate or (meth)acrylamide. More preferably, P_(g) ismethacrylate.

I-7. Preferred compounds of formulae I, I-1, I-2, I-3, I-4, I-5, and I-6include compounds of formula I-7, which are compounds of formula I, I-1,I-2, I-3, I-4, I-5, or I-6 wherein Y (a linking group) is alkylene,cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene),heteroarylene, oxaalkylene, thialkylene, alkyleneamine,alkylene-amide-alkylene, alkylene-amine-alkylene, or combinations of anyof the foregoing groups. Preferred linking groups include C₁-C₈ alkylene(e.g., ethylene or propylene), C₁-C₈ oxaalkylene, C₁-C₈ thialkylene,C₁-C₈ alkyleneamine, C₁-C₈ alkylene-amide-C₁-C₈ alkylene, and C₁-C₈alkylene-amine-C₁-C₈ alkylene. Particularly preferred are C₁-C₈oxaalkylene (e.g., —CH₂CH₂—O—), C₁-C₈ thialkylene (e.g., —CH₂CH₂—S—),and C₁-C₈ alkyleneamine (e.g., —CH₂CH₂—N(H)— or —CH₂CH₂—N(CH₃)—).

Specific examples of compounds of formula I include, but are not limitedto, the compounds shown in Table 1.

TABLE 1

2-((1-amino-8-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)oxy)ethylmethacrylate (Compound F)

N-(2-((1-amino-8-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)oxy)ethyl)methacrylamide

N-(2-((1-amino-8-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)oxy)ethyl)-N-methylmethacrylamide

2-((5-amino-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl methacrylate

N-(2-((5-amino-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)methacrylamide

N-(2-((5-amino-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)-N-methylmethacrylamide

2-((5-amino-1-methyl-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethylmethacrylate

N-(2-((5-amino-1-methyl-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)methacrylamide

N-(2-((5-amino-1-methyl-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)-N-methylmethacrylamide

2-((5-amino-4-oxochroman-6-yl)oxy)ethyl methacrylate (Compound M)

N-(2-((5-amino-4-oxochroman-6-yl)oxy)ethyl)methacrylamide

N-(2-((5-amino-4-oxochroman-6-yl)oxy)ethyl)-N-methylmethacrylamide

Compounds of formula I may be used in combination with other absorbingcompounds to provide desirable absorption characteristics. For example,preferred compositions may comprise a compound of formula I and a secondcompound that is a UV absorbing compound. UV absorbing compounds areknown in the art and fall into several classes which include, but arenot limited to, benzophenones, benzotriazoles, triazines, substitutedacrylonitriles, salicyclic acid derivatives, benzoic acid derivatives,cinnamic acid derivatives, chalcone derivatives, dypnone derivatives,crotonic acid derivatives, or any mixtures thereof. A preferred class ofUV absorbing compound is benzotriazoles, such as Norbloc(2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole).

A particularly preferred composition comprises2-(4-acetyl-3-amino-2,6-dimethoxyphenoxy)ethyl methacrylate and2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole.

Compounds of formula I may be prepared as shown in the followingreaction Scheme 1 and the associated description, as well as relevantliterature procedures that may be used by one of skill in the art.Exemplary reagents and procedures for these reactions appear in theworking examples.

Referring to Scheme 1, a commercially available7-substituted-3,4-dihydronaphthalen-1(2H)-one,6-substituted-chroman-4-one,6-substituted-2,3-dihydroquinolin-4(1H)-one,1-alkyl-6-substituted-2,3-dihydroquinolin-4(1H)-one, or similarcompound, wherein X is typically CH₂, O, S, NH, or NR, the substituentX′ is typically Cl, Br, or OCH₃, and R is a proton or methyl group, isconverted by a series of reactions including protection and deprotectionsteps into the corresponding amino 2-hydroxyethoxy derivative, such as8-amino-7-(2-hydroxyethoxy)-3,4-dihydronaphthalen-1(2H)-one,5-amino-6-(2-hydroxyethoxy)chroman-4-one,5-amino-6-(2-hydroxyethoxy)-2,3-dihydroquinolin-4(1H)-one, or5-amino-6-(2-hydroxyethoxy)-1-alkyl-2,3-dihydroquinolin-4(1H)-one, whichis subsequently acetylated with (meth)acrylic anhydride to form the(meth)acrylates of formula I. A different series of reactions includingprotection and deprotection steps can be used to synthesize thecorresponding amino 2-aminoethoxy derivatives that when acetylated with(meth)acrylic anhydride can form the (meth)acrylamides of formula I. Aswill be recognized by those skilled in the art, the above steps may bereadily modified as needed to provide the desired compounds. Thecompounds of formula I may also be made by other procedures other thanshown in Scheme 1.

High energy light absorbing compounds of formula I may be included inreactive mixtures to form various products, including biomedical devicesand ophthalmic devices. Generally, the high energy light absorbingcompounds can be present in any amount up to the limit of theirsolubility. For instance, the compounds may be present in an amount inthe range of about 0.1% to about 10% by weight, or from about 0.5 toabout 5% by weight, or from about 0.75% to about 4% by weight. The upperlimit is typically determined by the solubility of the compound withother co-monomers and or diluents in the reactive monomer mix.

Preferably, the high energy light absorbing compounds of the inventionare included in ophthalmic devices. A variety of ophthalmic devices maybe prepared, including hard contact lenses, soft contact lenses, cornealonlays, corneal inlays, intraocular lenses, or overlay lenses.Preferably, the ophthalmic device is a soft contact lens, which may bemade from conventional or silicone hydrogel formulations.

Ophthalmic devices of the invention comprise a free radical reactionproduct of a reactive mixture containing one or more compounds offormula I, one or more monomers suitable for making the desiredophthalmic device (also referred to herein as device forming monomers orhydrogel forming monomers), and optional components. Thus, the reactivemixture may, for example, include, in addition to compounds of formulaI, one or more of: hydrophilic components, hydrophobic components,silicone-containing components, wetting agents such as polyamides,crosslinking agents, and further components such as diluents andinitiators.

Hydrophilic Components

Examples of suitable families of hydrophilic monomers include(meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyllactams, N-vinyl amides, N-vinyl imides, N-vinyl ureas, O-vinylcarbamates, O-vinyl carbonates, other hydrophilic vinyl compounds, andmixtures thereof.

Non-limiting examples of hydrophilic (meth)acrylate and (meth)acrylamidemonomers include: acrylamide, N-isopropyl acrylamide,N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl acrylamide (DMA),2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl (meth)acrylate,3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate,2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate,4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl) (meth)acrylamide,N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N,N-bis(2-hydroxypropyl) (meth)acrylamide,N-(3-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl) (meth)acrylamide,N-(4-hydroxybutyl) (meth)acrylamide, 2-aminoethyl (meth)acrylate,3-aminopropyl (meth)acrylate, 2-aminopropyl (meth)acrylate,N-2-aminoethyl (meth)acrylamides), N-3-aminopropyl (meth)acrylamide,N-2-aminopropyl (meth)acrylamide, N,N-bis-2-aminoethyl(meth)acrylamides, N,N-bis-3-aminopropyl (meth)acrylamide),N,N-bis-2-aminopropyl (meth)acrylamide, glycerol methacrylate,polyethyleneglycol monomethacrylate, (meth)acrylic acid, vinyl acetate,acrylonitrile, and mixtures thereof.

Hydrophilic monomers may also be ionic, including anionic, cationic,zwitterions, betaines, and mixtures thereof. Non-limiting examples ofsuch charged monomers include (meth)acrylic acid,N-[(ethenyloxy)carbonyl]-β-alanine (VINAL), 3-acrylamidopropanoic acid(ACA1), 5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoicacid (AMBA), 2-(methacryloyloxy)ethyl trimethylammonium chloride (Q Saltor METAC), 2-acrylamido-2-methylpropane sulfonic acid (AMPS),1-propanaminium,N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, innersalt (CBT), 1-propanaminium,N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, innersalt (SBT), 3,5-Dioxa-8-aza-4-phosphaundec-10-en-1-aminium,4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT),2-methacryloyloxyethyl phosphorylcholine,3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate (DMVBAPS),3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS),3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate(MAMPDAPS),3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS),and methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate(MAPDAPS).

Non-limiting examples of hydrophilic N-vinyl lactam and N-vinyl amidemonomers include: N-vinyl pyrrolidone (NVP), N-vinyl-2-piperidone,N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-caprolactam,N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone,N-vinyl-4-methyl-2-caprolactam, N-vinyl-3-ethyl-2-pyrrolidone,N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl acetamide (NVA),N-vinyl-N-methylacetamide (VMA), N-vinyl-N-ethyl acetamide,N-vinyl-N-ethyl formamide, N-vinyl formamide,N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide,N-vinyl-2-methylpropionamide, N-vinyl-N,N′-dimethylurea,1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone; 1-ethyl-5-methylene-2-pyrrolidone,N-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,1-N-propyl-3-methylene-2-pyrrolidone,1-N-propyl-5-methylene-2-pyrrolidone,1-isopropyl-3-methylene-2-pyrrolidone,1-isopropyl-5-methylene-2-pyrrolidone, N-vinyl-N-ethyl acetamide,N-vinyl-N-ethyl formamide, N-vinyl formamide, N-vinyl isopropylamide,N-vinyl caprolactam, N-vinylimidazole, and mixtures thereof

Non-limiting examples of hydrophilic O-vinyl carbamates and O-vinylcarbonates monomers include N-2-hydroxyethyl vinyl carbamate andN-carboxy-β-alanine N-vinyl ester. Further examples of hydrophilic vinylcarbonate or vinyl carbamate monomers are disclosed in U.S. Pat. No.5,070,215. Hydrophilic oxazolone monomers are disclosed in U.S. Pat. No.4,910,277.

Other hydrophilic vinyl compounds include ethylene glycol vinyl ether(EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, and2-ethyl oxazoline.

The hydrophilic monomers may also be macromers or prepolymers of linearor branched poly(ethylene glycol), poly(propylene glycol), orstatistically random or block copolymers of ethylene oxide and propyleneoxide, having polymerizable moieties such as (meth)acrylates, styrenes,vinyl ethers, (meth)acrylamides, N-vinylamides, and the like. Themacromers of these polyethers have one polymerizable group; theprepolymers may have two or more polymerizable groups.

The preferred hydrophilic monomers of the present invention are DMA,NVP, HEMA, VMA, NVA, and mixtures thereof. Preferred hydrophilicmonomers include mixtures of DMA and HEMA. Other suitable hydrophilicmonomers will be apparent to one skilled in the art.

Generally, there are no particular restrictions with respect to theamount of the hydrophilic monomer present in the reactive monomermixture. The amount of the hydrophilic monomers may be selected basedupon the desired characteristics of the resulting hydrogel, includingwater content, clarity, wettability, protein uptake, and the like.Wettability may be measured by contact angle, and desirable contactangles are less than about 100°, less than about 80°, and less thanabout 60°. The hydrophilic monomer may be present in an amount in therange of, for instance, about 0.1 to about 100 weight percent,alternatively in the range of about 1 to about 80 weight percent,alternatively about 5 to about 65 weight percent, alternatively in therange of about 40 to about 60 weight percent, or alternatively about 55to about 60 weight percent, based on the total weight of the reactivecomponents in the reactive monomer mixture.

Silicone-Containing Components

Silicone-containing components suitable for use in the inventioncomprise one or more polymerizable compounds, where each compoundindependently comprises at least one polymerizable group, at least onesiloxane group, and one or more linking groups connecting thepolymerizable group(s) to the siloxane group(s). The silicone-containingcomponents may, for instance, contain from 1 to 220 siloxane repeatunits, such as the groups defined below. The silicone-containingcomponent may also contain at least one fluorine atom.

The silicone-containing component may comprise: one or morepolymerizable groups as defined above; one or more optionally repeatingsiloxane units; and one or more linking groups connecting thepolymerizable groups to the siloxane units. The silicone-containingcomponent may comprise: one or more polymerizable groups that areindependently a (meth)acrylate, a styryl, a vinyl ether, a(meth)acrylamide, an N-vinyl lactam, an N-vinylamide, anO-vinylcarbamate, an O-vinylcarbonate, a vinyl group, or mixtures of theforegoing; one or more optionally repeating siloxane units; and one ormore linking groups connecting the polymerizable groups to the siloxaneunits.

The silicone-containing component may comprise: one or morepolymerizable groups that are independently a (meth)acrylate, a(meth)acrylamide, an N-vinyl lactam, an N-vinylamide, a styryl, ormixtures of the foregoing; one or more optionally repeating siloxaneunits; and one or more linking groups connecting the polymerizablegroups to the siloxane units.

The silicone-containing component may comprise: one or morepolymerizable groups that are independently a (meth)acrylate, a(meth)acrylamide, or mixtures of the foregoing; one or more optionallyrepeating siloxane units; and one or more linking groups connecting thepolymerizable groups to the siloxane units.

Formula A.

The silicone-containing component may comprise one or more polymerizablecompounds of Formula A:

wherein:

at least one R^(A) is a group of formula R_(g)-L- wherein R_(g) is apolymerizable group and L is a linking group, and the remaining R^(A)are each independently:

-   -   (a) R_(g)-L-,    -   (b) C₁-C₁₆ alkyl optionally substituted with one or more        hydroxy, amino, amido, oxa, carboxy, alkyl carboxy, carbonyl,        alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or        combinations thereof,    -   (c) C₃-C₁₂ cycloalkyl optionally substituted with one or more        alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido,        carbamate, carbonate, halo, phenyl, benzyl, or combinations        thereof,    -   (d) a C₆-C₁₄ aryl group optionally substituted with one or more        alkyl, hydroxy, amino, amido, oxa, carboxy, alkyl carboxy,        carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl,        benzyl, or combinations thereof,    -   (e) halo,    -   (f) alkoxy, cyclic alkoxy, or aryloxy,    -   (g) siloxy,    -   (h) alkyleneoxy-alkyl or alkoxy-alkyleneoxy-alkyl, such as        polyethyleneoxyalkyl, polypropyleneoxyalkyl, or        poly(ethyleneoxy-co-propyleneoxyalkyl), or    -   (i) a monovalent siloxane chain comprising from 1 to 100        siloxane repeat units optionally substituted with alkyl, alkoxy,        hydroxy, amino, oxa, carboxy, alkyl carboxy, alkoxy, amido,        carbamate, halo or combinations thereof; and

n is from 0 to 500 or from 0 to 200, or from 0 to 100, or from 0 to 20,where it is understood that when n is other than 0, n is a distributionhaving a mode equal to a stated value. When n is 2 or more, the SiOunits may carry the same or different R^(A) substituents and ifdifferent R^(A) substituents are present, the n groups may be in randomor block configuration.

In Formula A, three R^(A) may each comprise a polymerizable group,alternatively two R^(A) may each comprise a polymerizable group, oralternatively one R^(A) may comprise a polymerizable group.

Formula B.

The silicone-containing component of formula A may be a mono-functionalpolymerizable compound of formula B:

wherein:

Rg is a polymerizable group;

L is a linking group;

j1 and j2 are each independently whole numbers from 0 to 220, providedthat the sum of j1 and j2 is from 1 to 220;

R^(A1), R^(A2), R^(A3), R^(A4), R^(A5), and R^(A7) are independently ateach occurrence C₁-C₆ alkyl, C₃-C₁₂ cycloalkyl, C₁-C₆ alkoxy, C₄-C₁₂cyclic alkoxy, alkoxy-alkyleneoxy-alkyl, aryl (e.g., phenyl), aryl-alkyl(e.g., benzyl), haloalkyl (e.g., partially or fully fluorinated alkyl),siloxy, fluoro, or combinations thereof, wherein each alkyl in theforegoing groups is optionally substituted with one or more hydroxy,amino, amido, oxa, carboxy, alkyl carboxy, carbonyl, alkoxy, carbamate,carbonate, halo, phenyl, or benzyl, each cycloalkyl is optionallysubstituted with one or more alkyl, hydroxy, amino, amido, oxa,carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl and eacharyl is optionally substituted with one or more alkyl, hydroxy, amino,amido, oxa, carboxy, alkyl carboxy, carbonyl, alkoxy, carbamate,carbonate, halo, phenyl, or benzyl; and

R^(A6) is siloxy, C₁-C₈ alkyl (e.g., C₁-C₄ alkyl, or butyl, or methyl),or aryl (e.g., phenyl), wherein alkyl and aryl may optionally besubstituted with one or more fluorine atoms.

Formula B-1.

Compounds of formula B may include compounds of formula B-1, which arecompounds of formula B wherein j1 is zero and j2 is from 1 to 220, or j2is from 1 to 100, or j2 is from 1 to 50, or j2 is from 1 to 20, or j2 isfrom 1 to 5, or j2 is 1.

B-2.

Compounds of formula B may include compounds of formula B-2, which arecompounds of formula B wherein j1 and j2 are independently from 4 to100, or from 4 to 20, or from 4 to 10, or from 24 to 100, or from 10 to100.

B-3.

Compounds of formulae B, B-1, and B-2 may include compounds of formulaB-3, which are compounds of formula B, B-1, or B-2 wherein R^(A1),R^(A2), R^(A3), and R^(A4) are independently at each occurrence C₁-C₆alkyl or siloxy. Preferred alkyl are C₁-C₃ alkyl, or more preferably,methyl. Preferred siloxy is trimethylsiloxy.

B-4.

Compounds of formulae B, B-1, B-2, and B-3 may include compounds offormula B-4, which are compounds of formula B, B-1, B-2, or B-3 whereinR^(A5) and R^(A7) are independently alkoxy-alkyleneoxy-alkyl, preferablythey are independently a methoxy capped polyethyleneoxyalkyl of formulaCH₃O—[CH₂CH₂O]_(p)—CH₂CH₂CH₂, wherein p is a whole number from 1 to 50.

B-5.

Compounds of formulae B, B-1, B-2, and B-3 may include compounds offormula B-5, which are compounds of formula B, B-1, B-2, or B-3 whereinR^(A5) and R^(A7) are independently siloxy, such as trimethylsiloxy.

B-6.

Compounds of formulae B, B-1, B-2, and B-3 may include compounds offormula B-6, which are compounds of formula B, B-1, B-2, or B-3 whereinR^(A5) and R^(A7) are independently C₁-C₆ alkyl, alternatively C₁-C₄alkyl, or alternatively, butyl or methyl.

B-7.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, and B-6 may includecompounds of formula B-7, which are compounds of formula B, B-1, B-2,B-3, B-4, B-5, or B-6 wherein R^(A6) is C₁-C₈ alkyl, preferably C₁-C₆alkyl, more preferably C₁-C₄ alkyl (for example methyl, ethyl, n-propyl,or n-butyl). More preferably R^(A6) is n-butyl.

B-8.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, and B-7, mayinclude compounds of formula B-8, which are compounds of formula B, B-1,B-2, B-3, B-4, B-5, B-6, or B-7 wherein Rg comprises styryl, vinylcarbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide,(meth)acrylate, or (meth)acrylamide. Preferably, Rg comprises(meth)acrylate, (meth)acrylamide, or styryl. More preferably, Rgcomprises (meth)acrylate or (meth)acrylamide. When Rg is(meth)acrylamide, the nitrogen group may be substituted with R^(A9),wherein R^(A9) is H, C₁-C₈ alkyl (preferably C₁-C₄ alkyl, such asn-butyl, n-propyl, methyl or ethyl), or C₃-C₈ cycloalkyl (preferablyC₅-C₆ cycloalkyl), wherein alkyl and cycloalkyl are optionallysubstituted with one or more groups independently selected fromhydroxyl, amide, ether, silyl (e.g., trimethylsilyl), siloxy (e.g.,trimethylsiloxy), alkyl-siloxanyl (where alkyl is itself optionallysubstituted with fluoro), aryl-siloxanyl (where aryl is itselfoptionally substituted with fluoro), and silyl-oxaalkylene- (where theoxaalkylene is itself optionally substituted with hydroxyl).

B-9.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, and B-8 mayinclude compounds of formula B-9, which are compounds of formula B, B-1,B-2, B-3, B-4, B-5, B-6, B-7, or B-8 wherein the linking group comprisesalkylene (preferably C₁-C₄ alkylene), cycloalkylene (preferably C₅-C₆cycloalkylene), alkyleneoxy (preferably ethyleneoxy), haloalkyleneoxy(preferably haloethyleneoxy), amide, oxaalkylene (preferably containing3 to 6 carbon atoms), siloxanyl, alkylenesiloxanyl, carbamate,alkyleneamine (preferably C₁-C₆ alkyleneamine), or combinations of twoor more thereof, wherein the linking group is optionally substitutedwith one or more substituents independently selected from alkyl,hydroxyl, ether, amine, carbonyl, siloxy, and carbamate.

B-10.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-10, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-siloxanyl-alkylene-alkyleneoxy-, oralkylene-siloxanyl-alkylene-[alkyleneoxy-alkylene-siloxanyl]_(q)-alkyleneoxy-,where q is from 1 to 50.

B-11.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-11, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis C₁-C₆ alkylene, preferably C₁-C₃ alkylene, more preferablyn-propylene.

B-12.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-12, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-carbamate-oxaalkylene. Preferably, the linking group isCH₂CH₂N(H)—C(═O)—O—CH₂CH₂—O—CH₂CH₂CH₂.

B-13.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-13, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis oxaalkylene. Preferably, the linking group is CH₂CH₂—O—CH₂CH₂CH₂.

B-14.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-14, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-[siloxanyl-alkylene]_(q)-, where q is from 1 to 50. Anexample of such a linking group is:—(CH₂)₃—[Si(CH₃)₂—O—Si(CH₃)₂—(CH₂)₂]_(q)—.

B-15.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-15, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkyleneoxy-carbamate-alkylene-cycloalkylene-carbamate-oxaalkylene,wherein cycloalkylene is optionally substituted with or 1, 2, or 3independently selected alkyl groups (preferably C₁-C₃ alkyl, morepreferably methyl). An example of such a linking group is—[OCH₂CH₂]_(q)—OC(═O)—NH—CH₂-[1,3-cyclohexylene]-NHC(═O)O—CH₂CH₂—O—CH₂CH₂—,wherein the cyclohexylene is substituted at the 1 and 5 positions with 3methyl groups.

B-16.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-16, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is a bond or is alkyleneoxy, wherein eachalkylene in alkyleneoxy is independently optionally substituted withhydroxyl. An example of such a linking group is —O—(CH₂)₃—. Anotherexample of such a linking group is —O—CH₂CH(OH)CH₂—O—(CH₂)₃—.

B-17.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-17, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is alkyleneamine. An example of such alinking group is —NH—(CH₂)₃—.

B-18.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-18, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis oxaalkylene optionally substituted with hydroxyl, siloxy, orsilyl-alkyleneoxy (where the alkyleneoxy is itself optionallysubstituted with hydroxyl). An example of such a linking group is—CH₂CH(G)CH₂—O—(CH₂)₃—, wherein G is hydroxyl. In another example, G isR³SiO— wherein two R groups are trimethylsiloxy and the third is C₁-C₈alkyl (preferably C₁-C₃ alkyl, more preferably methyl) or the third isC₃-C₈ cycloalkyl. In a further example, G isR³Si—(CH₂)₃—O—CH₂CH(OH)CH₂—O—, wherein two R groups are trimethylsiloxyand the third is C₁-C₈ alkyl (preferably C₁-C₃ alkyl, more preferablymethyl) or C₃-C₈ cycloalkyl. In a still further example, G is apolymerizable group, such as (meth)acrylate. Such compounds may functionas crosslinkers.

B-19.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-19, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is amine-oxaalkylene optionally substitutedwith hydroxyl. An example of such a linking group is—NH—CH₂CH(OH)CH₂—O—(CH₂)₃—.

B-20.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-20, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is alkyleneoxy-carbamate-oxaalkylene. Anexample of such a linking group is—O—(CH₂)₂—N(H)C(═O)O—(CH₂)₂—O—(CH₂)₃—.

B-21.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-21, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-carbamate-oxaalkylene. An example of such a linking group is—(CH₂)₂—N(H)C(═O)O—(CH₂)₂—O—(CH₂)₃—. Formula C. Silicone-containingcomponents of formulae A, B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8,B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-18, and B-21 may includecompounds of formula C, which are compounds of formula A, B, B-1, B-2,B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-13, B-14, B-15,B-18, or B-21 having the structure:

wherein

R^(A8) is hydrogen or methyl;

Z is O, S, or N(R^(A9)); and

L, j1, j2, R^(A1), R^(A2), R^(A3), R^(A4), R^(A5), R^(A6), R^(A7), andR^(A9) are as defined in formula B or its various sub-formulae (e.g.,B-1, B-2, etc.).

C-1.

Compounds of formula C may include (meth)acrylates of formula C-1, whichare compounds of formula C wherein Z is O.

C-2.

Compounds of formula C may include (meth)acrylamides of formula C-2,which are compounds of formula C wherein Z is N(R^(A9)), and R^(A9) isH.

C-3.

Compounds of formulae C may include (meth)acrylamides of formula C-3,which are compounds of formula C wherein Z is N(R^(A9)), and R^(A9) isC₁-C₈ alkyl that is unsubstituted or is optionally substituted asindicated above. Examples of R^(A9) include CH₃, —CH₂CH(OH)CH₂(OH),—(CH₂)₃-siloxanyl, —(CH₂)₃—SiR₃, and —CH₂CH(OH)CH₂—O—(CH₂)₃—SiR₃ whereeach R in the foregoing groups is independently selected fromtrimethylsiloxy, C₁-C₈ alkyl (preferably C₁-C₃ alkyl, more preferablymethyl), and C₃-C₈ cycloalkyl. Further examples of R^(A9) include:—(CH₂)₃—Si(Me)(SiMe₃)₂, and —(CH₂)₃—Si(Me₂)-[O—SiMe₂]₁₋₁₀—CH₃.

Formula D.

Compounds of formula C may include compounds of formula D:

wherein

R^(A8) is hydrogen or methyl;

Z¹ is O or N(R^(A9));

L¹ is alkylene containing 1 to 8 carbon atoms, or oxaalkylene containing3 to 10 carbon atoms, wherein L¹ is optionally substituted withhydroxyl; and

j2, R^(A3), R^(A4), R^(A5), R^(A6), R^(A7), and R^(A9) are as definedabove in formula B or its various sub-formulae (e.g., B-1, B-2, etc.).

D-1.

Compounds of formula D may include compounds of formula D-1, which arecompounds of formula D wherein L¹ is C₂-C₅ alkylene optionallysubstituted with hydroxyl. Preferably L¹ is n-propylene optionallysubstituted with hydroxyl.

D-2.

Compounds of formula D may include compounds of formula D-2, which arecompounds of formula D wherein L¹ is oxaalkylene containing 4 to 8carbon atoms optionally substituted with hydroxyl. Preferably L¹ isoxaalkylene containing five or six carbon atoms optionally substitutedwith hydroxyl. Examples include —(CH₂)₂—O—(CH₂)₃—, and—CH₂CH(OH)CH₂—O—(CH₂)₃—.

D-3.

Compounds of formulae D, D-1, and D-2 may include compounds of formulaD-3, which are compounds of formula D, D-1, or D-2 wherein Z¹ is O.

D-4.

Compounds of formulae D, D-1, and D-2 may include compounds of formulaD-4, which are compounds of formula D, D-1, or D-2 wherein Z¹ isN(R^(A9)), and R^(A9) is H.

D-5.

Compounds of formulae D, D-1, and D-2 may include compounds of formulaD-5, which are compounds of formula D, D-1, or D-2 wherein Z¹ isN(R^(A9)), and R^(A9) is C₁-C₄ alkyl optionally substituted with 1 or 2substituents selected from hydroxyl, siloxy, and C₁-C₆ alkyl-siloxanyl-.

D-6.

Compounds of formulae D, D-1, D-2, D-3, D-4, and D-5 may includecompounds of formula D-6, which are compounds of formula D, D-1, D-2,D-3, D-4, or D-5 wherein j2 is 1.

D-7.

Compounds of formulae D, D-1, D-2, D-3, D-4, and D-5 may includecompounds of formula D-7, which are compounds of formula D, D-1, D-2,D-3, D-4, or D-5 wherein j2 is from 2 to 220, or from 2 to 100, or from10 to 100, or from 24 to 100, or from 4 to 20, or from 4 to 10.

D-8.

Compounds of formulae D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 mayinclude compounds of formula D-8, which are compounds of formula D, D-1,D-2, D-3, D-4, D-5, D-6, or D-7 wherein R^(A3), R^(A4), R^(A5), R^(A6),and R^(A7) are independently C₁-C₆ alkyl or siloxy. Preferably R^(A3),R^(A4), R^(A5), R^(A6), and R^(A7) are independently selected frommethyl, ethyl, n-propyl, n-butyl, and trimethylsiloxy. More preferably,R^(A3), R^(A4), R^(A5), R^(A6), and R^(A7) are independently selectedfrom methyl, n-butyl, and trimethylsiloxy.

D-9.

Compounds of formulae D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 mayinclude compounds of formula D-9, which are compounds of formula D, D-1,D-2, D-3, D-4, D-5, D-6, or D-7 wherein R^(A3) and R^(A4) areindependently C₁-C₆ alkyl (e.g., methyl or ethyl) or siloxy (e.g.,trimethylsiloxy), and R^(A5), R^(A6), and R^(A7) are independently C₁-C₆alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl).

Formula E.

The silicone-containing component for use in the invention may comprisea multi-functional silicone-containing component. Thus, for example, thesilicone-containing component of formula A may comprise a bifunctionalmaterial of formula E:

wherein

Rg, L, j1, j2, R^(A1), R^(A2), R^(A3), R^(A4), R^(A5), and R^(A7) are asdefined above for formula B or its various sub-formulae (e.g., B-1, B-2,etc.);

L² is a linking group; and

Rg¹ is a polymerizable group.

E-1.

Compounds of formula E may include compounds of formula E-1, which arecompounds of formula E wherein Rg and Rg¹ are each a vinyl carbonate ofstructure CH₂═CH—O—C(═O)—O— or structure CH₂═C(CH₃)—O—C(═O)—O—.

E-2.

Compounds of formula E may include compounds of formula E-2, which arecompounds of formula E wherein Rg and Rg¹ are each (meth)acrylate.

E-3.

Compounds of formula E may include compounds of formula E-3, which arecompounds of formula E wherein Rg and Rg¹ are each (meth)acrylamide,wherein the nitrogen group may be substituted with R^(A9) (whereinR^(A9) is as defined above).

E-4.

Suitable compounds of formulae E, E-1, E-2, and E-3 include compounds offormula E-4, which are compounds of formula E, E-1, E-2, or E-3 whereinj1 is zero and j2 is from 1 to 220, or j2 is from 1 to 100, or j2 isfrom 1 to 50, or j2 is from 1 to 20.

E-5.

Suitable compounds of formulae E, E-1, E-2, and E-3 include compounds offormula E-5, which are compounds of formula E, E-1, E-2, or E-3, whereinj1 and j2 are independently from 4 to 100.

E-6.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, and E-5 includecompounds of formula E-6, which are compounds of formula E, E-1, E-2,E-3, E-4, or E-5 wherein R^(A1), R^(A2), R^(A3), R^(A4), and R^(A5) areindependently at each occurrence C₁-C₆ alkyl, preferably they areindependently C₁-C₃ alkyl, or preferably, each is methyl.

E-7.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, E-5, and E-6include compounds of formula E-7, which are compounds of formula E, E-1,E-2, E-3, E-4, E-5, or E-6 wherein R^(A7) is alkoxy-alkyleneoxy-alkyl,preferably it is a methoxy capped polyethyleneoxyalkyl of formulaCH₃O—[CH₂CH₂O]_(p)—CH₂CH₂CH₂, wherein p is a whole number from 1 to 50,or from 1 to 30, or from 1 to 10, or from 6 to 10.

E-8.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, E-5, E-6, and E-7include compounds of formula E-8, which are compounds of formula E, E-1,E-2, E-3, E-4, E-5, E-6, or E-7 wherein L comprises alkylene, carbamate,siloxanyl, cycloalkylene, amide, haloalkyleneoxy, oxaalkylene, orcombinations of two or more thereof, wherein the linking group isoptionally substituted with one or more substituents independentlyselected from alkyl, hydroxyl, ether, amine, carbonyl, and carbamate.

E-9.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, E-5, E-6, E-7, andE-8 include compounds of formula E-9, which are compounds of formula E,E-1, E-2, E-3, E-4, E-5, E-6, E-7, or E-8 wherein L² comprises alkylene,carbamate, siloxanyl, cycloalkylene, amide, haloalkyleneoxy,oxaalkylene, or combinations of two or more thereof, wherein the linkinggroup is optionally substituted with one or more substituentsindependently selected from alkyl, hydroxyl, ether, amine, carbonyl, andcarbamate.

Examples of silicone-containing components suitable for use in theinvention include, but are not limited to, compounds listed in Table 2.Where the compounds in Table 2 contain polysiloxane groups, the numberof SiO repeat units in such compounds, unless otherwise indicated, ispreferably from 3 to 100, more preferably from 3 to 40, or still morepreferably from 3 to 20.

TABLE 2 1 mono-methacryloxypropyl terminated mono-n-butyl terminatedpolydimethylsiloxanes (mPDMS) (preferably containing from 3 to 15 SiOrepeating units) 2 mono-acryloxypropyl terminated mono-n-butylterminated polydimethylsiloxane 3 mono(meth)acryloxypropyl terminatedmono-n-methyl terminated polydimethylsiloxane 4 mono(meth)acryloxypropylterminated mono-n-butyl terminated polydiethylsiloxane 5mono(meth)acryloxypropyl terminated mono-n-methyl terminatedpolydiethylsiloxane 6 mono(meth)acrylamidoalkylpolydialkylsiloxanes 7mono(meth)acryloxyalkyl terminated mono-alkyl polydiarylsiloxanes 83-methacryloxypropyltris(trimethylsiloxy)silane (TRIS) 93-methacryloxypropylbis(trimethylsiloxy)methylsilane 103-methacryloxypropylpentamethyl disiloxane 11mono(meth)acrylamidoalkylpolydialkylsiloxanes 12mono(meth)acrylamidoalkyl polydimethylsiloxanes 13N-(2,3-dihydroxypropane)-N′-(propyl tetra(dimethylsiloxy)dimethylbutylsilane)acrylamide 14N-[3-tris(trimethylsiloxy)silyl]-propyl acrylamide (TRIS-Am) 152-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propylmethacrylate (SiMAA) 162-hydroxy-3-methacryloxypropyloxypropyl-tris(trimethylsiloxy)silane 17

mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl terminated mono-n-butylterminated polydimethylsiloxanes (OH-mPDMS) (containing from 4 to 30, orfrom 4 to 20, or from 4 to 15 SiO repeat units) 18

19

20

21

22

23

24

Additional non-limiting examples of suitable silicone-containingcomponents are listed in Table 3. Unless otherwise indicated, j2 whereapplicable is preferably from 1 to 100, more preferably from 3 to 40, orstill more preferably from 3 to 15. In compounds containing j1 and j2,the sum of j1 and j2 is preferably from 2 to 100, more preferably from 3to 40, or still more preferably from 3 to 15.

TABLE 3 25

26

27

28

29

30 1,3-bis[4-(vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane 313-(vinyloxycarbonylthio) propyl-[tris (trimethylsiloxy)silane] 323-[tris(trimethylsiloxy)silyl] propyl allyl carbamate 333-[tris(trimethylsiloxy)silyl] propyl vinyl carbamate 34tris(trimethylsiloxy)silylstyrene (Styryl-TRIS) 35

36

37

38

39

40

41

Mixtures of silicone-containing components may be used. By way ofexample, suitable mixtures may include, but are not limited to: amixture of mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl terminatedmono-n-butyl terminated polydimethylsiloxane (OH-mPDMS) having differentmolecular weights, such as a mixture of OH-mPDMS containing 4 and 15 SiOrepeat units; a mixture of OH-mPDMS with different molecular weights(e.g., containing 4 and 15 repeat SiO repeat units) together with asilicone based crosslinker, such asbis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (ac-PDMS);a mixture of2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propylmethacrylate (SiMAA) and mono-methacryloxypropyl terminated mono-n-butylterminated polydimethylsiloxane (mPDMS), such as mPDMS 1000.

Silicone-containing components for use in the invention may have anaverage molecular weight of from about 400 to about 4000 daltons.

The silicone containing component(s) may be present in amounts up toabout 95 weight %, or from about 10 to about 80 weight %, or from about20 to about 70 weight %, based upon all reactive components of thereactive mixture (excluding diluents).

Polyamides

The reactive mixture may include at least one polyamide. As used herein,the term “polyamide” refers to polymers and copolymers comprisingrepeating units containing amide groups. The polyamide may comprisecyclic amide groups, acyclic amide groups and combinations thereof andmay be any polyamide known to those of skill in the art. Acyclicpolyamides comprise pendant acyclic amide groups and are capable ofassociation with hydroxyl groups. Cyclic polyamides comprise cyclicamide groups and are capable of association with hydroxyl groups.

Examples of suitable acyclic polyamides include polymers and copolymerscomprising repeating units of Formulae G1 and G2:

wherein X is a direct bond, —(CO)—, or —(CONHR₄₄)—, wherein R₄₄ is a C₁to C₃ alkyl group; R₄₀ is selected from H, straight or branched,substituted or unsubstituted C₁ to C₄ alkyl groups; R₄₁ is selected fromH, straight or branched, substituted or unsubstituted C₁ to C₄ alkylgroups, amino groups having up to two carbon atoms, amide groups havingup to four carbon atoms, and alkoxy groups having up to two carbongroups; R₄₂ is selected from H, straight or branched, substituted orunsubstituted C₁ to C₄ alkyl groups; or methyl, ethoxy, hydroxyethyl,and hydroxymethyl; R₄₃ is selected from H, straight or branched,substituted or unsubstituted C₁ to C₄ alkyl groups; or methyl, ethoxy,hydroxyethyl, and hydroxymethyl; wherein the number of carbon atoms inR₄₀ and R₄₁ taken together is 8 or less, including 7, 6, 5, 4, 3, orless; and wherein the number of carbon atoms in R₄₂ and R₄₃ takentogether is 8 or less, including 7, 6, 5, 4, 3, or less. The number ofcarbon atoms in R₄₀ and R₄₁ taken together may be 6 or less or 4 orless. The number of carbon atoms in R₄₂ and R₄₃ taken together may be 6or less. As used herein substituted alkyl groups include alkyl groupssubstituted with an amine, amide, ether, hydroxyl, carbonyl or carboxygroups or combinations thereof.

R₄₀ and R₄₁ may be independently selected from H, substituted orunsubstituted C₁ to C₂ alkyl groups. X may be a direct bond, and R₄₀ andR₄₁ may be independently selected from H, substituted or unsubstitutedC₁ to C₂ alkyl groups. R₄₂ and R₄₃ can be independently selected from H,substituted or unsubstituted C₁ to C₂ alkyl groups, methyl, ethoxy,hydroxyethyl, and hydroxymethyl.

The acyclic polyamides of the present invention may comprise a majorityof the repeating units of Formula LV or Formula LVI, or the acyclicpolyamides can comprise at least 50 mole percent of the repeating unitof Formula G or Formula G1, including at least 70 mole percent, and atleast 80 mole percent. Specific examples of repeating units of Formula Gand Formula G1 include repeating units derived fromN-vinyl-N-methylacetamide, N-vinylacetamide,N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide,N-vinyl-2-methylpropionamide, N-vinyl-N,N′-dimethylurea, N,N-dimethylacrylamide, methacrylamide, and acyclic amides of Formulae G2and G3:

Examples of suitable cyclic amides that can be used to form the cyclicpolyamides of include α-lactam, β-lactam, γ-lactam, δ-lactam, andε-lactam. Examples of suitable cyclic polyamides include polymers andcopolymers comprising repeating units of Formula G4:

wherein R₄₅ is a hydrogen atom or methyl group; wherein f is a numberfrom 1 to 10; wherein X is a direct bond, —(CO)—, or —(CONHR₄₆)—,wherein R₄₆ is a C₁ to C₃ alkyl group. In Formula LIX, f may be 8 orless, including 7, 6, 5, 4, 3, 2, or 1. In Formula G4, f may be 6 orless, including 5, 4, 3, 2, or 1. In Formula G4, f may be from 2 to 8,including 2, 3, 4, 5, 6, 7, or 8. In Formula LIX, f may be 2 or 3. WhenX is a direct bond, f may be 2. In such instances, the cyclic polyamidemay be polyvinylpyrrolidone (PVP).

The cyclic polyamides of the present invention may comprise 50 molepercent or more of the repeating unit of Formula G4, or the cyclicpolyamides can comprise at least 50 mole percent of the repeating unitof Formula G4, including at least 70 mole percent, and at least 80 molepercent.

The polyamides may also be copolymers comprising repeating units of bothcyclic and acyclic amides. Additional repeating units may be formed frommonomers selected from hydroxyalkyl(meth)acrylates,alkyl(meth)acrylates, other hydrophilic monomers and siloxanesubstituted (meth)acrylates. Any of the monomers listed as suitablehydrophilic monomers may be used as co-monomers to form the additionalrepeating units. Specific examples of additional monomers which may beused to form polyamides include 2-hydroxyethyl (meth)acrylate, vinylacetate, acrylonitrile, hydroxypropyl (meth)acrylate, methyl(meth)acrylate and hydroxybutyl (meth)acrylate, dihydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, and the like andmixtures thereof. Ionic monomers may also be included. Examples of ionicmonomers include (meth)acrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine(VINAL, CAS #148969-96-4), 3-acrylamidopropanoic acid (ACA1),5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoic acid(AMBA), 2-(methacryloyloxy)ethyl trimethylammonium chloride (Q Salt orMETAC), 2-acrylamido-2-methylpropane sulfonic acid (AMPS),1-propanaminium,N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, innersalt (CBT, carboxybetaine; CAS 79704-35-1), 1-propanaminium,N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, innersalt (SBT, sulfobetaine, CAS 80293-60-3),3,5-Dioxa-8-aza-4-phosphaundec-10-en-1-aminium,4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT,phosphobetaine, CAS 163674-35-9, 2-methacryloyloxyethylphosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate(DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate(AMPDAPS),3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate(MAMPDAPS),3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS),methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (MAPDAPS).

The reactive monomer mixture may comprise both an acyclic polyamide anda cyclic polyamide or copolymers thereof. The acyclic polyamide can beany of those acyclic polyamides described herein or copolymers thereof,and the cyclic polyamide can be any of those cyclic polyamides describedherein or copolymers thereof. The polyamide may be selected from thegroup polyvinylpyrrolidone (PVP), polyvinylmethyacetamide (PVMA),polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA),poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers andmixtures thereof. The polyamide may be a mixture of PVP (e.g., PVP K90)and PVMA (e.g., having a Mw of about 570 KDa).

The total amount of all polyamides in the reactive mixture may be in therange of between 1 weight percent and about 35 weight percent, includingin the range of about 1 weight percent to about 15 weight percent, andin the range of about 5 weight percent to about 15 weight percent, inall cases, based on the total weight of the reactive components of thereactive monomer mixture.

Without intending to be bound by theory, when used with a siliconehydrogel, the polyamide functions as an internal wetting agent. Thepolyamides of the present invention may be non-polymerizable, and inthis case, are incorporated into the silicone hydrogels assemi-interpenetrating networks. The polyamides are entrapped orphysically retained within the silicone hydrogels. Alternatively, thepolyamides of the present invention may be polymerizable, for example aspolyamide macromers or prepolymers, and in this case, are covalentlyincorporated into the silicone hydrogels. Mixtures of polymerizable andnon-polymerizable polyamides may also be used.

When the polyamides are incorporated into the reactive monomer mixturethey may have a weight average molecular weight of at least 100,000daltons; greater than about 150,000; between about 150,000 to about2,000,000 daltons; between about 300,000 to about 1,800,000 daltons.Higher molecular weight polyamides may be used if they are compatiblewith the reactive monomer mixture.

Cross-Linking Agents

It is generally desirable to add one or more cross-linking agents, alsoreferred to as cross-linking monomers, multi-functional macromers, andprepolymers, to the reactive mixture. The cross-linking agents may beselected from bifunctional crosslinkers, trifunctional crosslinkers,tetrafunctional crosslinkers, and mixtures thereof, includingsilicone-containing and non-silicone containing cross-linking agents.Non-silicone-containing cross-linking agents include ethylene glycoldimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA),trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC),glycerol trimethacrylate, methacryloxyethyl vinylcarbonate (HEMAVc),allylmethacrylate, methylene bisacrylamide (MBA), and polyethyleneglycol dimethacrylate wherein the polyethylene glycol has a molecularweight up to about 5000 Daltons. The cross-linking agents are used inthe usual amounts, e.g., from about 0.000415 to about 0.0156 mole per100 grams of reactive Formulas in the reactive mixture. Alternatively,if the hydrophilic monomers and/or the silicone-containing componentsare multifunctional by molecular design or because of impurities, theaddition of a cross-linking agent to the reactive mixture is optional.Examples of hydrophilic monomers and macromers which can act as thecross-linking agents and when present do not require the addition of anadditional cross-linking agent to the reactive mixture include(meth)acrylate and (meth)acrylamide endcapped polyethers. Othercross-linking agents will be known to one skilled in the art and may beused to make the silicone hydrogel of the present invention.

It may be desirable to select crosslinking agents with similarreactivity to one or more of the other reactive components in theformulation. In some cases, it may be desirable to select a mixture ofcrosslinking agents with different reactivity in order to control somephysical, mechanical or biological property of the resulting siliconehydrogel. The structure and morphology of the silicone hydrogel may alsobe influenced by the diluent(s) and cure conditions used.

Multifunctional silicone-containing components, including macromers,cross-linking agents, and prepolymers, may also be included to furtherincrease the modulus and retain tensile strength. The siliconecontaining cross-linking agents may be used alone or in combination withother cross-linking agents. An example of a silicone containingcomponent which can act as a cross-linking agent and, when present, doesnot require the addition of a crosslinking monomer to the reactivemixture includes α, ω-bismethacryloxypropyl polydimethylsiloxane.Another example is bis-3-acryloxy-2-hydroxypropyloxypropylpolydimethylsiloxane (ac-PDMS).

Cross-linking agents that have rigid chemical structures andpolymerizable groups that undergo free radical polymerization may alsobe used. Non-limiting examples of suitable rigid structures includecross-linking agents comprising phenyl and benzyl ring, such are1,4-phenylene diacrylate, 1,4-phenylene dimethacrylate,2,2-bis(4-methacryloxyphenyl)-propane,2,2-bis[4-(2-acryloxyethoxy)phenyl]propane,2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)-phenyl]propane, and4-vinylbenzyl methacrylate, and combinations thereof. Rigid crosslinkingagents may be included in amounts between about 0.5 and about 15, or2-10, 3-7 based upon the total weight of all of the reactive components.The physical and mechanical properties of the silicone hydrogels of thepresent invention may be optimized for a particular use by adjusting thecomponents in the reactive mixture.

Non-limiting examples of silicone cross-linking agents also include themulti-functional silicone-containing components described above, such ascompounds of Formula E (and its sub-formulae) and the multi-functionalcompounds shown in Table 3.

Further Constituents

The reactive mixture may contain additional components such as, but notlimited to, diluents, initiators, UV absorbers, visible light absorbers,photochromic compounds, pharmaceuticals, nutraceuticals, antimicrobialsubstances, tints, pigments, copolymerizable dyes, nonpolymerizabledyes, release agents, and combinations thereof.

Classes of suitable diluents for silicone hydrogel reactive mixturesinclude alcohols having 2 to 20 carbon atoms, amides having 10 to 20carbon atoms derived from primary amines and carboxylic acids having 8to 20 carbon atoms. The diluents may be primary, secondary, and tertiaryalcohols.

Generally, the reactive components are mixed in a diluent to form areactive mixture. Suitable diluents are known in the art. For siliconehydrogels, suitable diluents are disclosed in WO 03/022321 and U.S. Pat.No. 6,020,445, the disclosure of which is incorporated herein byreference. Classes of suitable diluents for silicone hydrogel reactivemixtures include alcohols having 2 to 20 carbons, amides having 10 to 20carbon atoms derived from primary amines, and carboxylic acids having 8to 20 carbon atoms. Primary and tertiary alcohols may be used. Preferredclasses include alcohols having 5 to 20 carbons and carboxylic acidshaving 10 to 20 carbon atoms. Specific diluents which may be usedinclude 1-ethoxy-2-propanol, diisopropylaminoethanol, isopropanol,3,7-dimethyl-3-octanol, 1-decanol, 1-dodecanol, 1-octanol, 1-pentanol,2-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol,tert-amyl alcohol, tert-butanol, 2-butanol, 1-butanol,2-methyl-2-pentanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-1-butanol,(3-acetoxy-2-hydroxypropyloxy)-propylbis(trimethylsiloxy) methylsilane,1-tert-butoxy-2-propanol, 3,3-dimethyl-2-butanol, tert-butoxyethanol,2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid,2-(diisopropylamino)ethanol mixtures thereof and the like. Examples ofamide diluents include N,N-dimethyl propionamide and dimethyl acetamide.

Preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol,1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol,3-methyl-3-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol,2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, ethanol,3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, decanoic acid, octanoicacid, dodecanoic acid, mixtures thereof and the like.

More preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol,1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol,1-dodecanol, 3-methyl-3-pentanol, 1-pentanol, 2-pentanol, t-amylalcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol,2-ethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, mixturesthereof and the like. If a diluent is present, generally there are noparticular restrictions with respect to the amount of diluent present.When diluent is used, the diluent may be present in an amount in therange of about 2 to about 70 weight percent, including in the range ofabout 5 to about 50 weight percent, and in the range of about 15 toabout 40 weight percent, based on the total weight of the reactivemixtures (including reactive and nonreactive Formulas). Mixtures ofdiluents may be used.

A polymerization initiator may be used in the reactive mixture. Thepolymerization initiator may include, for instance, at least one oflauroyl peroxide, benzoyl peroxide, isopropyl percarbonate,azobisisobutyronitrile, and the like, that generate free radicals atmoderately elevated temperatures, and photoinitiator systems such asaromatic alpha-hydroxy ketones, alkoxyoxybenzoins, acetophenones,acylphosphine oxides, bisacylphosphine oxides, and a tertiary amine plusa diketone, mixtures thereof and the like. Illustrative examples ofphotoinitiators are 1-hydroxycyclohexyl phenyl ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide(DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide (Irgacure819), 2,4,6-trimethylbenzyldiphenyl phosphine oxide and2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ester anda combination of cam-phorquinone and ethyl4-(N,N-dimethylamino)benzoate.

Commercially available (from IGM Resins B.V., The Netherlands) visiblelight initiator systems include Irgacure® 819, Irgacure® 1700, Irgacure®1800, Irgacure® 819, Irgacure® 1850 and Lucrin® TPO initiator.Commercially available (from IGM Resins B.V.) UV photoinitiators includeDarocur® 1173 and Darocur® 2959. These and other photoinitiators whichmay be used are disclosed in Volume III, Photoinitiators for FreeRadical Cationic & Anionic Photopolymerization, 2nd Edition by J. V.Crivello & K. Dietliker; edited by G. Bradley; John Wiley and Sons; NewYork; 1998. The initiator is used in the reactive mixture in effectiveamounts to initiate photopolymerization of the reactive mixture, e.g.,from about 0.1 to about 2 parts by weight per 100 parts of reactivemonomer mixture. Polymerization of the reactive mixture can be initiatedusing the appropriate choice of heat or visible or ultraviolet light orother means depending on the polymerization initiator used.Alternatively, initiation can be conducted using e-beam without aphotoinitiator. However, when a photoinitiator is used, the preferredinitiators are bisacylphosphine oxides, such asbis(2,4,6-tri-methylbenzoyl)-phenyl phosphine oxide (Irgacure® 819) or acombination of 1-hydroxycyclohexyl phenyl ketone andbis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide(DMBAPO).

While the compounds of formula I are the preferred high energy lightabsorbing compounds for use in the invention, other high energy lightabsorbing compounds are described in the examples and may be used aloneor in combination with the compounds of formula I. These include, forinstance, compounds of formula II, II-1, compound III, or combinationsthereof:

wherein Y is a linking group and P_(g) is a polymerizable group.Preferably Y is a bond. Preferably, Pg is vinyl. Preferred compounds offormula II include compounds of formula II-1:

Compound III: 1-(2-amino-3-methoxyphenyl)-2-methylprop-2-en-1-one.

The reactive mixture for making the ophthalmic devices of the inventionmay comprise, in addition to one or more high energy light absorbingcompounds, any of the other polymerizable compounds and optionalcomponents described above.

Preferred reactive mixtures may comprise: a high energy light absorbingcompound of formula I and a hydrophilic component.

Preferred reactive mixtures may comprise: a high energy light absorbingcompound of formula I and a hydrophilic component selected from DMA,NVP, HEMA, VMA, NVA, methacrylic acid, and mixtures thereof. Preferredare mixtures of HEMA and methacrylic acid.

Preferred reactive mixtures may comprise: a high energy light absorbingcompound of formula I, a hydrophilic component, and asilicone-containing component.

Preferred reactive mixtures may comprise: a high energy light absorbingcompound of formula I, a hydrophilic component, and asilicone-containing component comprising a compound of formula D (or itssub-formulae, such as D-1, D-2, etc.).

Preferred reactive mixtures may comprise: a high energy light absorbingcompound of formula I, a hydrophilic component selected from DMA, NVP,HEMA, VMA, NVA, and mixtures thereof; a silicone-containing componentcomprising a compound of formula D (or its sub-formulae, such as D-1,D-2, etc.); and an internal wetting agent.

Preferred reactive mixtures may comprise: a high energy light absorbingcompound of formula I, a hydrophilic component selected from DMA, HEMAand mixtures thereof; a silicone-containing component selected from2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propylmethacrylate (SiMAA), mono-methacryloxypropyl terminated mono-n-butylterminated polydimethylsiloxane (mPDMS),mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminatedmono-n-butyl terminated polydimethylsiloxane (OH-mPDMS), and mixturesthereof; and a wetting agent (preferably PVP or PVMA). For thehydrophilic component, mixtures of DMA and HEMA are preferred. For thesilicone containing component, mixtures of SiMAA and mPDMS arepreferred.

Preferred reactive mixtures may comprise: a high energy light absorbingcompound of formula I, a hydrophilic component comprising a mixture ofDMA and HEMA; a silicone-containing component comprising a mixture ofOH-mPDMS having from 2 to 20 repeat units (preferably a mixture of 4 and15 repeat units). Preferably, the reactive mixture further comprises asilicone-containing crosslinker, such as ac-PDMS. Also preferably, thereactive mixture contains a wetting agent (preferably DMA, PVP, PVMA ormixtures thereof).

The foregoing reactive mixtures may contain optional ingredients suchas, but not limited to, one or more initiators, internal wetting agents,crosslinkers, other UV or HEV absorbers, and diluents.

Curing of Hydrogels and Manufacture of Lens

The reactive mixtures may be formed by any of the methods known in theart, such as shaking or stirring, and used to form polymeric articles ordevices by known methods. The reactive components are mixed togethereither with or without a diluent to form the reactive mixture.

For example, ophthalmic devices may be prepared by mixing reactivecomponents, and, optionally, diluent(s), with a polymerization initiatorand curing by appropriate conditions to form a product that can besubsequently formed into the appropriate shape by lathing, cutting, andthe like. Alternatively, the reactive mixture may be placed in a moldand subsequently cured into the appropriate article.

A method of making a molded ophthalmic device, such as a siliconehydrogel contact lens, may comprise: preparing a reactive monomermixture; transferring the reactive monomer mixture onto a first mold;placing a second mold on top the first mold filled with the reactivemonomer mixture; and curing the reactive monomer mixture by free radicalcopolymerization to form the silicone hydrogel in the shape of a contactlens.

The reactive mixture may be cured via any known process for molding thereactive mixture in the production of contact lenses, includingspincasting and static casting. Spincasting methods are disclosed inU.S. Pat. Nos. 3,408,429 and 3,660,545, and static casting methods aredisclosed in U.S. Pat. Nos. 4,113,224 and 4,197,266. The contact lensesof this invention may be formed by the direct molding of the siliconehydrogels, which is economical, and enables precise control over thefinal shape of the hydrated lens. For this method, the reactive mixtureis placed in a mold having the shape of the final desired siliconehydrogel and the reactive mixture is subjected to conditions whereby themonomers polymerize, thereby producing a polymer in the approximateshape of the final desired product.

After curing, the lens may be subjected to extraction to removeunreacted components and release the lens from the lens mold. Theextraction may be done using conventional extraction fluids, suchorganic solvents, such as alcohols or may be extracted using aqueoussolutions.

Aqueous solutions are solutions which comprise water. The aqueoussolutions of the present invention may comprise at least about 20 weightpercent water, or at least about 50 weight percent water, or at leastabout 70 weight percent water, or at least about 95 weight percentwater. Aqueous solutions may also include additional water solubleFormulas such as inorganic salts or release agents, wetting agents, slipagents, pharmaceutical and nutraceutical Formulas, combinations thereofand the like. Release agents are compounds or mixtures of compoundswhich, when combined with water, decrease the time required to release acontact lens from a mold, as compared to the time required to releasesuch a lens using an aqueous solution that does not comprise the releaseagent. The aqueous solutions may not require special handling, such aspurification, recycling or special disposal procedures.

Extraction may be accomplished, for example, via immersion of the lensin an aqueous solution or exposing the lens to a flow of an aqueoussolution. Extraction may also include, for example, one or more of:heating the aqueous solution; stirring the aqueous solution; increasingthe level of release aid in the aqueous solution to a level sufficientto cause release of the lens; mechanical or ultrasonic agitation of thelens; and incorporating at least one leaching or extraction aid in theaqueous solution to a level sufficient to facilitate adequate removal ofunreacted components from the lens. The foregoing may be conducted inbatch or continuous processes, with or without the addition of heat,agitation or both.

Application of physical agitation may be desired to facilitate leach andrelease. For example, the lens mold part to which a lens is adhered canbe vibrated or caused to move back and forth within an aqueous solution.Other methods may include ultrasonic waves through the aqueous solution.

The lenses may be sterilized by known means such as, but not limited to,autoclaving.

As indicated above, preferred ophthalmic devices are contact lenses,more preferably soft hydrogel contact lenses. The transmissionwavelengths and percentages described herein may be measured on variousthicknesses of lenses using, for instance, the methodologies describedin the Examples. By way of example, a preferred center thickness formeasuring transmission spectra in a soft contact lens may be from 80 to100 microns, or from 90 to 100 microns or from 90 to 95 microns.Typically, the measurement may be made at the center of the lens using,for instance, a 4 nm instrument slit width. Various concentrations ofthe one or more polymerizable high energy light absorbing compounds maybe used to achieve the transmission characteristics described above. Forinstance, the concentration may be in the range of at least 1 percent,or at least 2 percent; and up to 10 percent, or up to 5 percent, basedon the weight percentages of all components in the reactive mixture,excluding diluent. A typical concentration may be in the range of 3 to 5percent.

Silicone hydrogel ophthalmic devices (e.g., contact lenses) according tothe invention preferably exhibit the following properties. All valuesare prefaced by “about,” and the devices may have any combination of thelisted properties. The properties may be determined by methods known tothose skilled in the art, for instance as described in United Statespre-grant publication US20180037690, which is incorporated herein byreference.

[H₂O] %: at least 20%, or at least 25% and/or up to 80% or up to 70%

Haze: 30% or less, or 10% or less

Kruss DCA (°): 1000 or less, or 50° or less

Tensile Modulus (psi): 120 or less, or 80 to 120

Dk (barrers): at least 80, or at least 100, or at least 150, or at least200

Elongation to Break: at least 100

For ionic silicon hydrogels, the following properties may also bepreferred (in addition to those recited above):

Lysozyme uptake (μg/lens): at least 100, or at least 150, or at least500, or at least 700

Polyquaternium 1 (PQ1) uptake (%): 15 or less, or 10 or less, or 5 orless

Some embodiments of the invention will now be described in detail in thefollowing Examples.

EXAMPLES

Test Methods

Ultraviolet-visible spectra of organic compounds in solution weremeasured on a Perkin Elmer Lambda 45 or an Agilent Cary 6000i UV/VISscanning spectrometer. The instrument was thermally equilibrated for atleast thirty minutes prior to use. For the Perkin Elmer instrument, thescan range was 200-800 nm; the scan speed was 960 nm per minute; theslit width was 4 nm; the mode was set on transmission or absorbance; andbaseline correction was selected. For the Cary instrument, the scanrange was 200-800 nm; the scan speed was 600 nm/min; the slit width was2 nm; the mode was transmission or absorbance; and baseline correctionwas selected. A baseline correction was performed before samples wereanalyzed using the autozero function.

Ultraviolet-visible spectra of contact lenses formed in part from theclaimed compositions were measured on a Perkin Elmer Lambda 45 UV/VIS oran Agilent Cary 6000i UV/VIS scanning spectrometer using packingsolution. The instrument was thermally equilibrated for at least thirtyminutes prior to use. For the Perkin Elmer instrument, the scan rangewas 200-800 nm; the scan speed was 960 nm per minute; the slit width was4 nm; the mode was set on transmission; and baseline correction wasselected. Baseline correction was performed using cuvettes containingplastic two-piece lens holders and the same solvents. These two-piececontact lens holders were designed to hold the sample in the quartzcuvette in the location through which the incident light beam traverses.The reference cuvette also contained a two-piece holder. To ensure thatthe thickness of the samples is constant, all lenses were made usingidentical molds. The center thickness of the contact lens was measuredusing an electronic thickness gauge. Reported center thickness andpercent transmission spectra are obtained by averaging three individuallens data.

It is important to ensure that the outside surfaces of the cuvette arecompletely clean and dry and that no air bubbles are present in thecuvette. Repeatability of the measurement is improved when the referencecuvette and its lens holder remain constant and when all samples use thesame sample cuvette and its lens holder, making sure that both cuvettesare properly inserted into the instrument.

EXAMPLES

The following abbreviations will be used throughout the Examples andFigures and have the following meanings:

AlCl₃: aluminum chloride

NBS: N-bromosuccinimide

FeCl₃: iron (III) chloride

DIAD: diisopropyl azodicarboxylate

PPh₃: triphenylphosphine

Cs₂CO₃: cesium carbonate

XantPhos: 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene

Pd₂(dba)₃:

HCl: hydrochloric acid

DMAP: dimethylaminopyridine

Pd(dppf)₂C₁₂:

KOAc: potassium acetate

AcOH: acetic acid

H₂O₂: hydrogen peroxide

KNO₃: potassium nitrate

THF: tetrahydrofuran

Pd/C: palladium on carbon

H₂: hydrogen gas

L: liter(s)

mL: milliliter(s)

Equiv. or eq.: equivalent(s)

LCMS: Liquid chromatography-mass spectroscopy

kg: kilogram(s)

g: gram(s)

mol: mole(s)

mmol: millimole(s)

TLC: thin layer chromatography

1H NMR: proton nuclear magnetic resonance spectroscopy

UV-VIS: ultraviolet-visible spectroscopy

psi: pounds per square inch

HNO₃: nitric acid

TsOH: p-toluenesulfonic acid

HCl: hydrochloric acid

Et₃N: triethylamine

CH₂Cl₂ or DCM: dichloromethane

SnCl₂: tin (II) chloride or stannous chloride

EtOH: ethanol

Na₂CO₃: sodium carbonate

EtOAc: ethyl acetate

BHT: 2,6-bis(1,1-dimethylethyl)-4-methylphenol

CDCl₃: deutro-chloroform

Cs₂CO₃: cesium or caesium carbonate

NaHCO₃: sodium bicarbonate

Na₂SO₄: sodium sulfate

K₂CO₃: potassium carbonate

DMSO: dimethyl sulfoxide

3-chloropropiophenone (Sigma-Aldrich)

1-(3-hydroxy-4-nitrophenyl)-ethan-1-one (Combi-Blocks)

1-(4-hydroxy-3-nitrophenyl)-ethan-1-one (Combi-Blocks)

Da: dalton or g/mole

kDa: kilodalton or an atomic mass unit equal to 1,000 daltons

DMA: N, N-dimethylacrylamide (Jarchem)

HEMA: 2-hydroxyethyl methacrylate (Bimax)

PVP: poly(N-vinylpyrrolidone) (ISP Ashland)

PDMA: polydimethylacrylamide

PVMA: polyvinylmethyacetamide

EGDMA: ethylene glycol dimethacrylate (Esstech)

TEGDMA: tetraethylene glycol dimethacrylate (Esstech)

TMPTMA: trimethylolpropane trimethacrylate (Esstech)

Tegomer V-Si 2250: diacryloxypolydimethylsiloxane (Evonik)

Irgacure 1700: mixture of 25% bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphineoxide and 75% 2-hydroxy-2-methyl-1-phenyl-propan-1-one(BASF)

Irgacure 819: bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (BASF orCiba Specialty Chemicals)

Irgacure 1870: blend ofbis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphineoxide and1-hydroxy-cyclohexyl-phenyl-ketone (BASF or Ciba Specialty Chemicals)

mPDMS: mono-n-butyl terminated monomethacryloxypropyl terminatedpolydimethylsiloxane (M_(n)=800-1000 daltons) (Gelest)

HO-mPDMS: mono-n-butyl terminatedmono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminatedpolydimethylsiloxane (M_(n)=400-1500 daltons) (Ortec or DSM-PolymerTechnology Group)

SiMAA: 2-propenoic acid,2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propylester (Toray) or3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropylmethacrylate

Norbloc®: 2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole(Janssen)

Blue HEMA:1-amino-4-[3-(4-(2-methacryloyloxy-ethoxy)-6-chlorotriazin-2-ylamino)-4-sulfophenylamino]anthraquinone-2-sulfonicacid, as described in U.S. Pat. No. 5,944,853

RB247: 1,4-Bis[2-methacryloxyethylamino]-9,10-anthraquinone Bisomer IMTBlue or C.I. Reactive Blue 69: 2-anthracenesulfonic acid,1-amino-4-[[4-[(2-bromo-1-oxo-2-propen-1-yl)amino]-2-sulfophenyl]amino]-9,10-dihydro-9,10-dioxo-,sodium salt (1:2) or 2-anthracenesulfonic acid,1-amino-4-[[4-[(2-bromo-1-oxo-2-propenyl)amino]-2-sulfophenyl]amino]-9,10-dihydro-9,10-dioxo-,disodium salt (9CI) (Geo Specialty Chemicals) or disodiumN-[4-[(4-amino-9,10-dioxo-3-sulfoanthracen-1-yl)amino]-3-sulfonatophenyl]-2-bromoprop-2-enimidate(CAS #70209-99-3)D30: 3,7-dimethyl-3-octanol (Vigon)DIW: deionized waterMeOH: methanolIPA: isopropyl alcoholBC: back or base curve plastic mold made from PP, TT, Z or blendsthereofFC: front curve plastic mold from PP, TT, Z or blends thereofPP: polypropylene which is the homopolymer of propyleneTT: Tuftec which is a hydrogenated styrene butadiene block copolymer(Asahi Kasei Chemicals)Z: Zeonor which is a polycycloolefin thermoplastic polymer (Nippon ZeonCo Ltd)TL03 lights: Phillips TLK 40 W/03 bulbsLED: light emitting diodeRMM: reactive monomer mixture(s)NaH: sodium hydrideBAGE: Boric Acid Glycerol Ester (molar ratio of boric acid to glycerolwas 1:2) 299.3 grams (mol) of glycerol and 99.8 grams (mol) of boricacid were dissolved in 1247.4 grams of a 5% (w/w) aqueous EDTA solutionin a suitable reactor and then heated with stirring to 90-94° C. undermild vacuum (2-6 torr) for 4-5 hours and allowed to cool down to roomtemperature. Borate Buffered Packing Solution: 18.52 grams (300 mmol) ofboric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28grams (197 mmol) of sodium sulfate were dissolved in enough deionizedwater to fill a 2 liter volumetric flask.

Example 1—Synthesis of Compound (F) as Shown in Scheme 2

7-Hydroxy-3,4-dihydronaphthalen-1 (2H)-one (A)

A suspension of 7-methoxy-3,4-dihydronaphthalen-1(2H)-one (334.0 grams,1.90 moles, 1.0 equiv.) and anhydrous aluminum chloride (782 grams, 5.86moles, 3.1 equiv.) in anhydrous toluene (8 L) was heated at 85° C. for30 minutes, at which point LCMS indicated the reaction was complete. Theblack reaction mixture was cooled to 0° C. and poured into ice/watermixture (8.7 L) and stirred 5 minutes. The product was extracted withethyl acetate (3×7 L). The combined organic layers were washed withwater (2×1.7 L) and saturated brine (1.7 L). The organic layer wasconcentrated under reduced pressure. The residue was triturated withtoluene (2.5 L) overnight. The solids were filtered, rinsed with toluene(0.9 L) and heptanes (0.9 L) to give compound (A) (301 g, 97%yield, >95% purity) as a beige solid. Prior to conversion into compound(B), compound (A) was purified as follows: compound (A) (195.4 grams)was purified over silica gel (200 grams), eluting with ethyl acetate (16L). The solid was dried under vacuum at 40° C. overnight to givecompound (A) (192 grams, 94% yield, >95% purity).

8-Bromo-7-hydroxy-3,4-dihydronaphthalen-1(2H)-one (B)

Ferric chloride (1.9 grams, 11.8 mmol, 0.01 equiv.) was added to astirred suspension of compound (A) (191 grams, 1.18 moles, 1.0 equiv.)and N-bromosuccinimide (209.5 grams, 1.18 moles, 1.0 equiv.) inanhydrous acetonitrile (1.9 L), resulting in a mild exotherm (10° C.increase in temperature). After stirring for 16 hours, water (7 L) wasadded, and the reaction mixture was stirred for one hour. The resultingsolid was filtered and washed with water (2×2.3 L). The solid wasdissolved in ethyl acetate (3.4 L) and washed with water (1 L). Theorganic solvent was concentrated under reduced pressure, and the residuewas purified over silica gel (3 kg), eluting with a gradient of 0 to 10%ethyl acetate in dichloromethane. The solid was dried under vacuum at40° C. overnight to give compound (B) (147 grams, 52% yield, >97%purity) as a light-yellow solid.

8-Bromo-7-(2-(tert-butoxy)ethoxy)-3,4-dihydronaphthalen-1(2H)-one (C)

A solution of diisopropyl azodicarboxylate (697 grams, 3.45 moles, 3.5equiv, DIAD) in anhydrous THF (3.4 L) was added over 30 minutes to asolution of triphenyl-phosphine (900 grams, 3.44 moles, 3.5 equiv.) inTHF (6.6 L) at 0° C. After stirring for 45 minutes, a white precipitatewas observed. A solution of compound (B) (238 grams, 0.98 moles, 1.00equiv.), ethylene glycol mono-tert-butyl ether (147 grams, 1.24 moles,1.25 equiv.) in THF (1.7 L) was added over 30 minutes. The cooling bathwas removed, and the reaction mixture was stirred at room temperatureovernight, at which point LCMS indicated 30% of compound (B) remained.The tetrahydrofuran was removed under reduced pressure. The residue wasdissolved in toluene (18 L) and was washed sequentially with 2N sodiumhydroxide (2×9 L) and saturated brine (2×4.4 L). The combined aqueouswashes were extracted with ethyl acetate (9 L). The combined organiclayers were concentrated under reduced pressure. The residue waspurified by five passes through a Biotage 150 cartridge, eluting with agradient of 0 to 20% ethyl acetate in heptanes to give compound (C) (421grams, 55% yield, 44% purity by ¹H-NMR). Note: The compound at thispoint contains both reduced DIAD and DIAD, neither of which effect thenext reaction and are readily removed by chromatography in the nextstep.

N-(2-(2-(tert-Butoxy)ethoxy)-8-oxo-5,6,7,8-tetrahydronaphthalen-1-yl)acet-amide(D)

A suspension of compound (C) (193 grams, 567 mmol, 1.0 equiv.),acetamide (67 grams, 1.13 mol, 2.0 equiv) and cesium carbonate (555grams, 1.7 mol, 3 equiv.) in 1,4-dioxane (15 L) was sparged withnitrogen for 15 minutes. XantPhos (16.4 grams, 28 mmol, 0.05 equiv.) andPd₂(dba)₃ (10.2 grams, 11.2 mmol, 0.02 equiv.) were added. The reactionmixture was sparged with nitrogen for an additional 5 minutes. Afterrefluxing for 1.5 hours, the reaction was cooled to 30° C. andconcentrated under reduced pressure to a volume of ˜1.5 L. Ethyl acetate(48 L) was added, and the resulting mixture was washed with saturatedbrine (7.4 L). The organic layer was dried over sodium sulfate, filteredand concentrated under reduced pressure. The residue was purified oversilica gel (1.5 kg) eluting with a gradient of 0 to 80% ethyl acetate inheptanes to yield compound (D) (75.5 grams, 42% yield) as a pale yellowsolid.

8-Amino-7-(2-hydroxyethoxy)-3,4-dihydronaphthalen-1(2H)-one (E)

Compound (D) (25 grams, 0.078 mol, 1.0 equiv.) in aqueous HCl (3 M, 750mL) was heated to 80° C. for 3.5 hours at which point LCMS indicatecomplete deprotection. The reaction was cooled to room temperature, andsolid sodium carbonate was added in portions until a pH of 10 wasobtained. Dichloromethane (250 mL) was added, and the mixture wasstirred for ˜10 minutes. Two reactions of the same scale were combinedin a separatory funnel, and additional dichloromethane (250 mL) wasadded. The layers were separated, and the aqueous layer was backextracted with dichloromethane (250 mL). The combined organic layerswere concentrated under reduced pressure to give crude compound (E)(43.8 grams, >85% purity by LCMS) as brown oil which was usedsubsequently.

2-((1-Amino-8-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)oxy)ethylmethacrylate (F)

Crude compound (E) (43.8 grams, ˜85% purity, ˜0.133 mol, 1.0 equiv) andDMAP (5 grams, 0.041 mol, 0.3 equiv.) in dichloromethane (800 mL) werestirred under nitrogen for 10 minutes. A solution of methacrylicanhydride (21.5 grams, 0.144 mol, 1.08 equiv.) and dichloromethane (125mL) was added over a period of 30 minutes. An exotherm of ˜4° C. wasobserved over the course of the addition. After stirring at roomtemperature over a weekend, saturated sodium bicarbonate (400 mL) wasadded, and the layers were separated. The aqueous layer was backextracted with dichloromethane (200 mL). The combined organic layerswere washed with saturated brine (250 mL) and concentrated under reducedpressure. The residue was purified over silica gel (450 grams), elutingwith a gradient of 0 to 15% ethyl acetate in heptanes. The product wasdried under vacuum at 40° C. for 24 hours to give compound (F) (25.0grams, 55% yield from compound (D)) as a yellow solid (MP=90.7° C.). ¹HNMR (500 MHz, CDCl₃) δ 1.96 (3H, s, CH₃), 2.02 (2H, m, cyclic-H), 2.61(2H, t, J=6.0 Hz, cyclic-H), 2.83 (2H, t, J=6.0 Hz, cyclic-H), 4.22 (2H,t, J=5.0 Hz, CH₂), 4.53 (2H, t, J=5.0 Hz, CH₂), 5.60 (1H, m, vinylic),6.14 (1H, m, vinylic), 6.37 (1H, d, J=7.5 Hz, Ar—H), 6.79 (1H, d, J=7.5Hz, Ar—H). The UV-VIS spectrum of compound (F) in a 0.2 mM methanolsolution is shown in FIG. 1.

Example 2—Synthesis of Compound (M) as Shown in Scheme 3

6-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)chroman-4-one (G)

A mixture 6-bromo chroman-4-one (100.85 grams, 444.156 mmol, 1 equiv.),potassium acetate (130.77 grams, 1332.467 mmol, 3 equiv.) andbis(pinacolato)diboron (135.35 grams, 532.985 mmol, 1.2 equiv.) in1,4-dioxane was sparged with nitrogen for 30 minutes.[1,1′-Bis-(diphenylphosphino)ferrocene]dichloropalladium(II) complex(18.14 grams, 22.208 mmol, 0.05 equiv.) in dichloromethane was added,and the mixture was heated at 95° C. overnight. After cooling to roomtemperature, the mixture was filtered through Celite, and the filtercake was washed with ethyl acetate (2×500 mL). The filtrate was washedwith water (500 mL) and saturated brine (500 mL). The combined aqueouslayers were back-extracted with ethyl acetate (2×300 mL). The combinedorganic layers were dried over sodium sulfate, filtered, andconcentrated under reduced pressure. The residue was purified on aBiotage-75 column, eluting with a gradient of 0 to 50% ethyl acetate inheptanes, to give compound (G) (151.82 grams, theoretical yield 121.75grams) as a light-brown oil, which contained somebis(pinacolato)-diboron. This material was used in the preparation of(H).

6-Hydroxychroman-4-one (H)

Acetic acid (150 mL) was added to a solution of compound (G) (151.8grams, ˜444.15 mmol, 1 equiv.) in THF (750 mL) and water (225 mL) atroom temperature. After stirring at room temperature for 1 hour, 30%hydrogen peroxide in water (150 mL) was added in portions to themixture, and the resulting mixture was stirred at room temperatureovernight. After cooling in an ice-bath, a 20% aqueous sodium sulfite(800 mL) was added dropwise (peroxide testing paper was negative). Themixture was extracted with ethyl acetate (3×800 mL), and the combinedorganic layers were washed with saturated brine (800 mL), dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified twice on a flash Biotage-75 column, eluting eachtime with a gradient of 0 to 50% ethyl acetate in heptanes to givecompound (H) (59.7 grams, 82% yield for 2 steps) as a light-yellowsolid.

6-Hydroxy-5-nitrochroman-4-one (I)

A solution of compound (H) (10 grams, 60.916 mmol, 1 equiv.) in diethylether (1000 mL) was added in portions to a mixture of sodium nitrate(5.177 grams, 60.916 mmol, 1 equiv.) and lanthanum(III) nitratehexahydrate (2.637 grams, 6.092 mmol, 0.1 equiv.) in 6M HCl (200 mL).The mixture was stirred at room temperature for 41 hours at which timethe mixture became a reddish solution, and TLC showed that the startingmaterial was consumed. The mixture was transferred to a separatoryfunnel, and the layers were separated. The aqueous layer was extractedwith ethyl acetate (3×200 mL). The combined organic layers were washedwith water (500 mL), saturated brine (500 mL), dried over sodiumsulfate, filtered, and concentrated under reduced pressure. The residuewas purified on an AnaLogix automated column system (220 grams silicagel column), eluting with a gradient of 0 to 60% ethyl acetate inheptanes to give compound (I) (2.4 grams, 19% yield, 85% purity with a15% bis-nitro by-product) as a yellow solid. The reaction should bemonitored and stopped when the reaction is deemed complete by TLC, andthen immediately worked-up to isolate the desired product; otherwise thebis-nitro by-product may become the major product.

6-(2-(tert-Butoxy)ethoxy)-5-nitrochroman-4-one (J)

Triphenylphosphine (18.81 grams, 71.715 mmol, 1.5 equiv.) anddiisopropyl azodicarboxylate (DIAD, 14.12 mL, 71.715 mmol, 1.5 equiv)were added sequentially to a solution of compound (I) (10 grams, 47.81mmol, 1 equiv.) and ethyleneglycol mono-t-butyl ether (6.28 mL, 47.81mmol, 1 equiv.) in anhydrous THF (500 mL) at room temperature. Afterstirring at room temperature overnight, the mixture was concentratedunder reduced pressure. The residue was purified twice on an AnaLogixautomated column system (330 grams silica gel column), eluting each timewith a gradient of 0 to 100% ethyl acetate in heptanes to give compound(J) (16.3 grams, theoretical yield 14.79 grams) as a yellow solid, whichcontained some reduced DIAD. This material was used in the preparationof compound (K).

5-Amino-6-(2-(tert-butoxy)ethoxy)chroman-4-one (K)

A mixture of compound (J) (15.5 grams) which contained some reduced DIADand 10% palladium on carbon (1.55 grams) in ethanol (1100 mL) washydrogenated at 20 psi at room temperature for 6 hours. LCMS indicatedthat a mixture of compound (K) (80%) and an over-reduced by-product(20%) was formed.

Another batch of compound (J) (4 grams) was hydrogenated at 15 psi. LCMSindicated that a mixture of compound (K) (95%) and an over-reducedby-product (5%) was formed. The two batches were combined for work-up.The mixture was filtered through Celite, and the filter cake was washedwith ethanol (200 mL). The filtrate was concentrated under reducedpressure. The residue was purified on an AnaLogix automated columnsystem (330 grams silica gel column), eluting with a gradient of 0 to40% ethyl acetate in heptanes to give compound (K) (7.8 grams, 13% yieldfor 3 steps) as a yellow oil.

5-Amino-6-(2-hydroxyethoxy)chroman-4-one (L)

A mixture of compound (K) (7.8 grams, 27.923 mmol, 1 equiv.) in 6M HCl(100 mL) was stirred at room temperature for 3 hours at which point LCMSindicated that the reaction was complete. The mixture was cooled in anice-bath, and solid sodium carbonate was carefully added in portionsuntil the pH was 10. The mixture was diluted with ethyl acetate (400 mL)and water (200 mL). The layers were separated, and the aqueous layer wasextracted with ethyl acetate (2×100 mL). The combined organic layerswere washed with saturated brine (200 mL), dried over sodium sulfate,filtered and concentrated under reduced pressure to give compound (L)(5.77 grams, 90% yield) as a yellow solid, which was used in thepreparation of (M).

2-((5-Amino-4-oxochroman-6-yl)oxy)ethyl methacrylate (M)

Methacrylic anhydride (4.15 mL, 27.841 mmol, 1.1 equiv.) was addeddropwise to a solution of compound (L) (5.65 grams, 25.31 mmol, 1equiv.) and DMAP (0.93 grams, 7.593 mmol, 0.3 equiv.) in anhydrousdichloromethane (300 mL) at room temperature. After stirring at roomtemperature overnight, the mixture was washed with saturated sodiumbicarbonate (100 mL) and saturated brine solution (100 mL). The combinedaqueous layers were back-extracted with dichloromethane (2×100 mL). Thecombined organic layers were dried over sodium sulfate, filtered, andconcentrated under reduced pressure. The residue was purified on anAnaLogix automated column system (120 grams silica gel column), elutingwith a gradient of 0 to 30% ethyl acetate in heptanes to give compound(M) (6.0 grams, 80% yield) as a sticky yellow solid. ¹H NMR (500 MHz,CDCl₃) δ 1.93 (3H, s, CH₃), 2.70 (2H, t, J=5.5 Hz, CH₂), 4.22 (2H, t,J=5.5 Hz, CH₂), 4.41 (2H, t, J=6.1 Hz, CH₂), 4.53 (2H, t, J=6.1 Hz,CH₂), 5.60 (1H, m, vinylic), 6.11 (1H, d, J=8.2 Hz, Ar—H), 6.15 (1H, m,vinylic), 6.85 (1H, d, J=8.2 Hz, Ar—H). The UV-VIS spectrum of compound(M) in a 0.2 mM methanol solution is shown in FIG. 1.

Example 3 Synthesis of(Z)-3-hydroxy-1-(naphthalen-2-yl)-3-(4-vinylphenyl)prop-2-en-1-one (N)as Shown in Scheme 4

To a 250 mL round bottomed flask containing a magnetic stirring bar,methyl 4-vinylbenzoate (2 grams, 12.3 mmol) and NaH (4.9 grams, 10 eq.60% sodium hydride in oil suspension) were added. A pressure equalizingaddition funnel containing 50 mL of dried THF (molecular sieves) wasattached, and the reaction system purged with dry nitrogen gas for 20minutes. Thereafter, the THF was added slowly with vigorous stirring.2-Acetonaphthone (3.5 grams, 12.3 mmol) and a small amount ofhydroquinone were dissolved in 10 mL dried THF and added dropwise to thereaction mixture. The contents of the reaction vessel were stirred for12 hours. Then, the reaction flask was placed in an ice bath, andaqueous hydrochloric acid was added slowly to react with excess NaH. Thevolatile components were removed by rotary evaporation, and the residualdissolved/suspended in DCM. After filtration, the organic layer wasextracted with dichloromethane in a separatory funnel, washed withdilute hydrochloric acid and brine, and then dried over MgSO₄. Afterfiltration, the solvent was removed by rotary evaporation. The residualwas dissolved in ethyl acetate. The unreacted acetonaphthone was removedby precipitation into excess hexanes. The crude product was isolated byfiltration and rotary evaporation which was then further purified usinga silica column with ethyl acetate/hexane (1:5) as eluent, yielding(Z)-3-hydroxy-1-(naphthalen-2-yl)-3-(4-vinylphenyl)prop-2-en-1-one (N).¹H NMR (500 MHz, CDCl₃) δ 5.40 (1H, d, J=11.0 Hz, vinylic), 5.91 (1H, d,J=17.5 Hz, vinylic), 6.79 (1H, dd, J=11.0 Hz, J=17.5 Hz, vinylic), 6.99(1H, s, enol H—C═C—O—), 7.52-8.03 (10H, m, Ar—H), 8.54 (1H, s, Ar—H);note: the exchangeable enolic proton was not observed.

Example 4

Reactive monomer mixtures (RMM 1-4) were prepared, composed of 77 weightpercent of the formulations listed in Table 4, and 23 weight percent ofthe diluent D30. All components except the PVP were mixed in a jar undera nitrogen atmosphere at ambient temperature for about 90 minutes, afterwhich the PVP was added and mixed for about 240 minutes at ambienttemperature. Thereafter, the jar was capped and placed on a roller forabout 1000-6000 minutes at room temperature until a homogeneous solutionwas obtained, typically around 1500 to 1600 minutes. Ambient and roomtemperatures are typically between 25-30° C. The reactive monomermixtures were then filtered through a 3 μm filter using astainless-steel syringe under pressure. All reactive monomer mixtureswere degassed at ambient temperature by applying vacuum (40 torr) for 45minutes prior to making contact lenses.

TABLE 4 RMM 1 RMM 2 RMM 3 RMM 4 RMM 5 RMM 6 RMM 7 RMM 8 Component (wt.%) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) mPDMS 31.431.75 31.13 30.53 30.66 31.08 30.80 30.87 1000 SiMAA 28.35 28.66 28.127.57 27.49 28.07 27.82 27.78 DMA 24.31 24.58 24.1 23.63 23.69 24.0623.84 23.88 HEMA 6.08 6.15 6 5.91 6.00 5.93 5.92 5.97 TEGDMA 1.5 1.51.47 1.5 1.5 1.5 1.5 1.5 PVP K90 7 7 6.9 7 6.8 7 7.01 6.9 Irgacure 0.340.34 0.3 0.34 0.34 0.34 0.34 0.34 1870 Norbloc ® 1 0 0 1.5 1.5 0 0.750.75 Bisomer 0 0 0 0.02 0.02 0.02 0.02 0.02 IMT Blue Compound 0 0 2 2 00 1 0 (F) Compound 0 0 0 0 2 0 0 1 (M) Compound 0 0 0 0 0 2 1 1 (N) Σ100 100 100 100 100 100 100 100 Components

In a glove box with a nitrogen gas atmosphere and less than about 0.2percent oxygen gas, about 75-100 μL of the RMM 1 and RMM 2 were dosedseparately using an Eppendorf pipet at room temperature into the FC madeof 90:10 Z:TT blend. The BC made of 90:10 Z:TT blend was then placedonto the FC. The molds were equilibrated for a minimum of twelve hoursin the glove box prior to dosing. Trays containing eight mold assemblieseach were transferred into an adjacent glove box maintained at 63° C.,and a quartz plate was used to cover and secure the mold assemblies inthe trays. Lenses were cured from the top and the bottom for 10 minutesusing 435 nm LED lights having an intensity of about 2.1 mW/cm² at thetray's location.

The lenses were manually de-molded with most lenses adhering to the FCand released by suspending the lenses in about one liter of 70 percentIPA for about one or two hours, followed by washing two times with 70percent IPA and then three times with DI water. Each washing step lastedabout 30 minutes. The lenses were equilibrated in borate bufferedpackaging solution overnight and then stored in fresh borate bufferedpackaging solution thereafter. Lenses (4A) made from RMM 1 had anaverage center thickness of 87 microns. Lenses (4B) made from RMM 2 hadan average center thickness of 87 microns.

Lenses (4C) were prepared from RMM 3 using the same curing conditionsand hydration steps as used to make the previous lenses (4A and 4B)except that the curing time was 15 minutes. The average center thicknessof these lenses (4C) was 86 microns.

Lenses (4D) were prepared on a pilot line using RMM 4 and similar curingand hydration conditions as used to make the previous lenses (4A and 4B)except for the oxygen gas concentration was less than 3% and theirradiation conditions were 1.5 mW/cm² for about 5 minutes and then 2.5mW/cm² for about 10 minutes. The average center thickness of theselenses (4C) was 80 microns.

Lenses (4E) were prepared from RMM 5 using the same curing conditionsand hydration steps as used to make the previous lenses (4A and 4B)except that the curing conditions were 1.5 mW/cm² for about 5 minutesand then 2.5 mW/cm² for about 10 minutes at 65° C. The average centerthickness of these lenses (4E) was about 85 microns.

The UV-VIS transmission spectra of lenses (4A), (4B), (4C), (4D) and(4E) are shown in FIG. 2, demonstrating that silicone hydrogel contactlenses with about 2 weight percent of compound (F) or compound (M) andabout 1.5 weight percent Norbloc® exhibit complete absorption betweenabout 250 nm and about 400 nm while absorbing some blue light betweenabout 400 nm and about 450 nm. Compound (M) absorbed further into thevisible region than compound (F).

Example 5

Reactive monomer mixtures (RMM 6, RMM 7, and RMM 8) were prepared,composed of 77 weight percent of the formulations listed in Table 4, and23 weight percent of the diluent D30. All components except the PVP weremixed in a jar under a nitrogen atmosphere at ambient temperature forabout 90 minutes, after which the PVP was added and mixed for about 240minutes at ambient temperature. Thereafter, the jar was capped andplaced on a roller for about 1000-6000 minutes at room temperature untila homogeneous solution was obtained, typically around 1500 to 1600minutes. Ambient and room temperatures are typically between 25-30° C.The reactive monomer mixtures were then filtered through a 3 μm filterusing a stainless-steel syringe under pressure. All reactive monomermixtures were degassed at ambient temperature by applying vacuum (40torr) for 45 minutes prior to making contact lenses.

In a glove box with a nitrogen gas atmosphere and less than about 0.2percent oxygen gas, about 75-100 μL of the RMM 6, RMM 7, and RMM 8 weredosed separately using an Eppendorf pipet at room temperature into theFC made of 90:10 Z:TT blend. The BC made of 90:10 Z:TT blend was thenplaced onto the FC. The molds were equilibrated for a minimum of twelvehours in the glove box prior to dosing. Trays containing eight moldassemblies each were transferred into an adjacent glove box maintainedat 65° C., and a quartz plate was used to cover and secure the moldassemblies in the trays. Lenses were cured from the top and the bottomusing 1.0 mW/cm² for about 5 minutes and then 2.5 mW/cm² for about 10minutes using 435 nm LED lights.

The lenses were manually de-molded with most lenses adhering to the FCand released by suspending the lenses in about one liter of 70 percentIPA for about one or two hours, followed by washing two times with 70percent IPA and then three times with DI water. Each washing step lastedabout 30 minutes. The lenses were equilibrated in borate bufferedpackaging solution overnight and then stored in fresh borate bufferedpackaging solution thereafter. Lenses (5A) were made from RMM 6. Lenses(5B) were made from RMM 7. Lenses (5C) were made from RMM 8. The averagecenter thickness of these lenses (5A-5C) was about 85 microns.

The UV-VIS transmission spectra of lenses (4A), (5A), (5B), and (5C) areshown in FIG. 3, demonstrating that silicone hydrogel contact lenseswith 2 weight percent of compound (N) and no Norbloc® or with about 1weight percent of compound (N), about 1 weight percent of eithercompound (F) or compound (M), and 0.75 weight percent Norbloc® exhibitcomplete absorption between about 250 nm and about 400 nm whileabsorbing some HEV light between about 400 nm and about 450 nm.

Example 6

Reactive monomer mixtures (RMM 9 and RMM 10) were prepared, composed of52 weight percent of the formulation listed in Table 5, and 48 weightpercent of the diluent BAGE. The components were mixed in a jar under anitrogen atmosphere at ambient temperature. Thereafter, the jar wascapped and placed on a roller for about 1400 minutes at ambienttemperature until the reactive monomer mixture was homogeneous. Thereactive monomer mixture was then filtered through a 3 μm filter using astainless-steel syringe under pressure.

TABLE 5 RMM 9 RMM 10 Component Weight % Weight % HEMA 94.91 95.81 MAA1.94 1.95 EGDMA 0.77 0.79 TMPTMA 0.09 0.09 Blue HEMA 0.01 0.01 Irgacure1700 1.33 1.34 Norbloc ® 0.95 0 Σ Components 100 100

The reactive monomer mixtures RMM 9 and RMM 10 were degassed at ambienttemperature by applying vacuum (40 torr) for 45 minutes. Then, in aglove box with a nitrogen gas atmosphere and less than about 0.2 percentoxygen gas, about 75 μL of the reactive mixtures RMM 9 and RMM 10 wereseparately dosed using an Eppendorf pipet at room temperature into theFC made of 90:10 Z:TT blend. The BC made of 90:10 Z:TT blend was thenplaced onto the FC. The molds were equilibrated for a minimum of twelvehours in the glove box prior to dosing. Trays containing eight moldassemblies each were transferred into an adjacent glove box maintainedat 65° C., and a quartz plate was used to cover and secure the moldassemblies in the trays. Lenses were cured from the top and the bottomfor 8 minutes using 435 nm LED lights having an intensity of about 2.1mW/cm² at the tray's location. The lenses were manually de-molded withmost lenses adhering to the FC and released by suspending the lenses in30 percent IPA for about 30-60 minutes, followed by soaking in DIW for30 minutes and then in PS for 30 minutes. The lenses were still somewhattacky, so the lenses were soaked again in DIW and individually placed invials containing PS. Lenses (6A) were made from RRM 9 and had an averagecenter thickness of 86 microns. Lenses (6B) were made from RRM 10 andhad an average center thickness of 83 microns. A person of ordinaryskill recognizes that the exact lens release process can be varieddepending on the lens formulation and mold materials, regarding theconcentrations of the aqueous isopropanol solutions, the number ofwashings with each solvent, and the duration of each step. The purposeof the lens release process is to release all lenses without defects andtransition from diluent swollen networks to the packaging solutionswollen hydrogels.

45.9 Milligrams of compound (F) was dissolved in 4.4423 grams of RMM 9to yield a reactive monomer mixture containing about 2 weight percent ofcompound (F). Lenses (6C) were then prepared using the same curingconditions and hydration steps as used to make the previous lenses (6Aand 6B) except that the curing time was 15 minutes. The average centerthickness of these lenses (6C) was 87 microns.

45.6 Milligrams of compound (F) was dissolved in 4.4146 grams of RMM 10to yield a reactive monomer mixture containing about 2 weight percent ofcompound (F). Lenses (6D) were then prepared using the same curingconditions and hydration steps as used to make the previous lenses (6Aand 6B) except that the curing time was 15 minutes. The average centerthickness of these lenses (6D) was 84 microns.

56.5 Milligrams of compound (M) was dissolved in 5.1395 grams of RMM 9to yield a reactive monomer mixture containing about 2 weight percent ofcompound (M). There were some visible undissolved particles of compound(M) that were filtered off prior to making lenses. As a result, theconcentration of compound (M) may be less than 2 weight percent in thisformulation. Lenses (6E) were then prepared using the same curingconditions and hydration steps as used to make the previous lenses (6Aand 6B) except that the curing time was 15 minutes. The average centerthickness of these lenses (6C) was 91 microns.

The UV-VIS transmission spectra of lenses (6A), (6B), (6C), (6D), and(6E) are shown in FIG. 4, demonstrating that conventional hydrogelcontact lenses (6C) and (6E) with about 2 weight percent of compound (F)or compound (M) and about 1 weight percent Norbloc® exhibit nearlycomplete absorption between about 250 nm and about 400 nm whileabsorbing some blue light between about 400 nm and about 450 nm.Compound (M) absorbed further into the visible region than compound (F).Increasing the concentration of compound (F) or compound (M) in theformulation may provide complete absorption between about 250 nm andabout 400 nm while absorbing some blue light between about 400 nm andabout 450 nm.

We claim:
 1. An ophthalmic device that is a free radical reactionproduct of a reactive mixture comprising: one or more monomers suitablefor making the ophthalmic device; and a polymerizable high energy lightabsorbing compound comprising a compound of formula I:

wherein R¹, R² and R³ are independently H, C₁-C₆ alkyl, C₅-C₈cycloalkyl, C₁-C₆ alkoxy, aryl, aryloxy, halo, or —Y—P_(g); X is CR⁴R⁵,O, S, or NR⁴; R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently H, C₁-C₆alkyl, C₅-C₈ cycloalkyl, or —Y—P_(g); Y is a linking group; and P_(g) isa polymerizable group, wherein at least one of R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, and R⁹ is —Y—P_(g).
 2. The ophthalmic device of claim 1 whereinthe compound of formula I contains one —Y—P_(g) group.
 3. The ophthalmicdevice of claim 1 wherein R¹ is —Y—P_(g).
 4. The ophthalmic device ofclaim 1 wherein R² and R³ are each H.
 5. The ophthalmic device of claim1 wherein R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are each H.
 6. The ophthalmicdevice of claim 1 wherein X is CH₂, O, NH, or NCH₃.
 7. The ophthalmicdevice of claim 1 wherein Y comprises: C₁-C₈ alkylene, alkyleneoxy,C₁-C₈ oxaalkylene, C₁-C₈ thiaalkylene, C₁-C₈ alkylene-ester-C₁-C₈alkylene, C₁-C₈ alkylene-amide-C₁-C₈ alkylene, or C₁-C₈alkylene-amine-C₁-C₈ alkylene.
 8. The ophthalmic device of claim 1wherein P_(g) comprises: styryl, vinyl carbonate, vinyl ether, vinylcarbamate, N-vinyl lactam, N-vinylamide, (meth)acrylate, or(meth)acrylamide.
 9. The ophthalmic device of claim 1 further comprisinga second polymerizable high energy light absorbing compound.
 10. Theophthalmic device of claim 9 wherein the second polymerizable highenergy light absorbing compound is a UV absorbing compound.
 11. Theophthalmic device of claim 10 wherein the UV absorbing compoundcomprises a compound of formula I, a benzophenone, a benzotriazole, atriazine, a substituted acrylonitrile, a salicyclic acid derivative, abenzoic acid derivative, a cinnamic acid derivative, a chalconederivative, a dypnone derivative, a crotonic acid derivative, ormixtures thereof.
 12. The ophthalmic device of claim 9 wherein thesecond polymerizable high energy light absorbing compound is2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole,(Z)-3-hydroxy-1-(naphthalen-2-yl)-3-(4-vinylphenyl)prop-2-en-1-one,1-(2-amino-3-methoxyphenyl)-2-methylprop-2-en-1-one, or combinationsthereof.
 13. The ophthalmic device of claim 1 wherein the monomersuitable for making the ophthalmic device comprises a hydrophiliccomponent, a silicone-containing component, or mixtures thereof.
 14. Theophthalmic device of claim 1 that is a contact lens, a corneal onlay, acorneal inlay, an intraocular lens, or an overlay lens.
 15. Theophthalmic device of claim 1 that is a hydrogel contact lens.
 16. Amethod for making an ophthalmic device, the method comprising: (a)providing a reactive mixture containing a compound of formula I:

wherein R¹, R² and R³ are independently H, C₁-C₆ alkyl, C₅-C₈cycloalkyl, C₁-C₆ alkoxy, aryl, aryloxy, halo, or —Y—P_(g); X is CR⁴R⁵,O, S, or NR⁴; R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently H, C₁-C₆alkyl, C₅-C₈ cycloalkyl, or —Y—P_(g); Y is a linking group; and P_(g) isa polymerizable group, wherein at least one of R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, and R⁹ is —Y—P_(g); and one or more device forming monomers, anda radical initiator; and (b) polymerizing the reactive mixture to formthe ophthalmic device.
 17. A silicone hydrogel contact lens that is areaction product of a reactive mixture comprising: a polymerizable highenergy light absorbing compound of formula I:

wherein R¹, R² and R³ are independently H, C₁-C₆ alkyl, C₅-C₈cycloalkyl, C₁-C₆ alkoxy, aryl, aryloxy, halo, or —Y—P_(g); X is CR⁴R⁵,O, S, or NR⁴; R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently H, C₁-C₆alkyl, C₅-C₈ cycloalkyl, or —Y—P_(g); Y is a linking group; and P_(g) isa polymerizable group, wherein at least one of R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, and R⁹ is —Y—P_(g); and one or more monomers suitable for makingan ophthalmic device.
 18. The silicone hydrogel contact lens of claim 17wherein the contact lens has a contact angle of about 70° or less, awater content of at least 25 percent, and an oxygen permeability of atleast 80 barrers.
 19. A compound that is:2-((1-amino-8-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)oxy)ethylmethacrylate;N-(2-((1-amino-8-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)oxy)ethyl)methacrylamide;N-(2((1-amino-8-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)oxy)ethyl)-N-methylmethacrylamide;2-((5-amino-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethylmethacrylate;N-(2-((5-amino-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)methacrylamide;N-(2((5-amino-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)-N-methylmethacrylamide;2-((5-amino-1-methyl-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethylmethacrylate;N-(2-((5-amino-1-methyl-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)methacrylamide;N-(2-((5-amino-1-methyl-4-oxo-1,2,3,4-tetrahydroquinolin-6-yl)oxy)ethyl)-N-methylmethacrylamide;2-((5-amino-4-oxochroman-6-yl)oxy)ethyl methacrylate;N-(2-((5-amino-4-oxochroman-6-yl)oxy)ethyl)methacrylamide; orN-(2-((5-amino-4-oxochroman-6-yl)oxy)ethyl)-N-methylmethacrylamide.